Guillermo Gonzalez-Moraga

Cluster
Chemistry
Introduction to the Chemistry of Transition Metal
and Main Group Element Molecular Clusters

With 232 Figures

Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
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Unapter 2 For the benefit of clarity, this Chapter has been restricted fundamentally to
the discussion of the chemistry of molecular transition metal clusters : no
Transition Metal Cluster Chemistry Binuclear compounds, which were analyzed to some extent in Chapter 1, nor
nt icrocrystalline metal particles arc considered . For the same reason the main
emphasis is given to hmonuclear metal compounds . However, heteronuelear
s pccies with different transition metals or containing main group atoms are
taken into account whenever they are useful for a better understanding of cluster

The word cluster evokes the idea of a group, bunch, swelling, i .e c hemistry .
. the idea of a so The chemistry of cluster containing main group elements is discussed in
of equivalent individuals that through strong interactions
among themselves C'haptcrs 3 and 4 . Moreover, selected aspects of the chemistry of some iron-
can behave as a new entity clearly differentiated from the surroundings . tiulfur clusters of great biological interest are analyzed in Chapter 5 .
chemistry, cluster are fundamentally a group of atoms- in In the
the case of metal
clusters, of metal atoms-directly linked to each other leading to a polyatomi
metallic nucleus that can be
found either isolated or associated with a givenc
number of ligands . Some examples of this kind of compound are illustrated 2 .1 Classification of Clusters
Fig. 2.1 . in
Microerystalline metal particles are species that agree well with Molecular clusters may be classified by considering the presence and nature of
the defini-
tion of isolated clusters . Investigations in this field have grown significantly in the ligands they exhibit . There is first a non-ligand class of isolated molecular
the last few years promoted to a great extent by the importance of such kinds of cluster species known as naked clusters as those exemplified by the anions Pbs -
microcrystals for understanding and improving catalytic processes
. However or Sn5 - in Fig . 2 .1d . Strictly, naked clusters can be refered to only when these
they have been studied from a physical rather than from a chemical species are in a total inert medium or matrix . However the idea of naked can
view. Hence, the chemical knowledge about these systems is still point of
incipient . also be extended to species that existing in determined media, in solution or in
the solid state, their interactions with the environment are considerably smaller
c that those among the constituents of the cluster . The naked cluster ions of
c+ cl post-transition metals, which under determined conditions can be stabilized in
~~ jr/ solution or in solid compounds, can be included in this class of molecular
clusters . As mentioned above, the chemistry of this kind of compounds is
described in Chapter 4 . Nonetheless, most of the known molecular metal

~I oj/ C1 -Cl
clusters are not bare metal conglomerates but follow a pattern similar to that
found in classical metal complexes, i .e . a nucleus, consisting of, in this case,
a metal network surrounded by a given number of ligands . These clusters can be
cl
a b classified by the type of ligands they contain .
c
There are two large classes of molecular clusters in which the ligands are all
of the same nature : The halide cluster class and the carbonyl or, in general,
organometallic cluster class . According to the formal oxidation numbers ac-
S ` ~' S quired by metal atoms in these two classes of clusters, they are often classified as
316 high and low-valence clusters respectively .
In the high-valence cluster species, metal atoms forming the metal network
\ \per \ /\i appear to have positive intermediate oxidation states . However, metal oxidation
-,,I -'o',. states in cluster are always lower than those characteristic for the same metals in
d classical mononuclear complexes . The ligands associated to this class of cluster
e f are normally good rr-donors that according to the classification of Pearson
fig. 2.1 . Examples of different types of molecular dusters would have intermediate hardness . Among these compounds the most frequent
[Pt 19(COt, Z J'" , (c) [MohCl,] . Cluster of (a) [Rh 9 (COj21 P]3 ,
4 . (d) Pbs (e) Fe,S,(NO)a , (f) Nit (triphos)1(p- ( b)
7 3- P3J 2 CO
are the halides, specially chlorides and bromides . An example of this cluster class
groups have been removed for clarity
is the molybdenum species [Mo h X s ] °+ shown in Fig . 2 .1c .


2 Tanitin Metal Clute Chemity 2 .1 Claificatin f Clute 57

56

• • will be een in the numeu examle f metal clute dicued in the next
ectin, the multitude f binding ibilitie ffeed by ganic ligand ae in
° P at enible f the vaiety f ecie and tuctue beved f -
,.A- °~ ganmetallic mlecula dwte.
c

44
C-0
C Cabn mnxide. A mentined eviuly, the mt imtant ganic ligand
P P in lw-valence metal clute i by fa cabn mnxide . It i actically the nly
ii ne that i able t fm binay clute cmund, M mL 0 . Meve, almt all
° metal clute cntaining the ganic ligand ae al metal cabnyl . Until
• • P nw, thee have been vey few the binay ganmetal clute . Mt f them
ae icyanide deivative, a ligand vey imila t cabn mnxide .
a b Stuctual deteminatin hw that the CO-ligand in metal dute can be
bnded t the metal cnglmeate fundamentally in the thee mde illutated
chematically in Fig . 2 .3 .
P
. 1 . Tw-cente  teminal cabnyl ( t -CO) . The CO-gu i bnded t ne

/ \
P
P ~ vetex f metal lyhedn .O
BndmayM C-
be linea  bent .
0 0 2. Thee-cente  edge-bidging cabnyl (u 2 -CO). The CO-gu i bnded
 C c, `C imultaneuly t tw neighbu atm in a metal lyhedn . The detectin
C0
  f bidging cabnyl gu ften indicate the eence f metal-metal
~, C0 bnd .
C
. CO 3. Fu-centeed  tiangula face-bidging cabnyl (j4 3 -CO) . The CO-gu
OC
CO i bnded t thee metal atm haing a face f the lyhedn .
c c
0
OC C  A futh mde f CO-cdinatin i al knwn, namely that fund in the
P C0 anin [Fe4(CO), 3 H] - in which, a can be beved in Fig. 2A, ne cabn
mnxide ligand i cdinated by the cabn atm t all fu Fe-atm which
C d ae aanged in a buttefly cnfiguatin . A al indicated in Fig . 2 .4, the
CO-xygen atm aea t be al bnded t the metal lyhedn .
.-
Fig. 22 Examle f diffeent tye f Iw •v alence mlecula clute f) ,,,
RU(CO){nCl (b)
Pta(CO)S [PPh(Me_)),, (c) C,(PPh 3 ),(PPh) a , (d) Ru .C(CO)„(C,H,Me,) While teminal and edge-bidged CO-ligand ae nmally fund in mnuc-
lea and binuclea cabnyl cmlexe eectively, the face-bidging mde i
chaacteitic f clute cmlexe and, the bigge the nucleaity f the clute,
the me fequently 3-CO ligand ae fund .
Lw-valence clute ae ecie in which the metal atm have an xidatin Bidged CO ligand ae cmmnly beved f the fit and ecnd-w
tate ze  negative . They ae alway aciated with ligand able t behave a tanitin metal cmlexe but they ae hweve ae in neutal thid-w metal
it-accet . Sme examle f clute belnging thi cla ae hwn in Fig . 2 .2 .
Cabn mnxide i by fa the mt eeentative f thee ligand but thee ac
al many examle f cmund cntaining the tyical ft ligand uch a C
hhine, lefine, acetylene, cyclentadiene . etc . 0 0
C C

2 .1 .1 Tye f Ligand
a a
A&.
b
OP* c
!n the next ectin,cua atilltith
cue difft ncleaity and hae will be
weenu
analyzed . Hweve, fitly, it i cnvenient t examine biefly the diffeent tye Fig. 23. Mde f bnding f cabn mnxide in metal clute t) Teminal, (b) edge-bidging.
f ligand a well a the mde in which they ae bnded t metal clute. A (c) face-bidging


58 2 Transition Metal Cluster Chemistry 2.1 Classification of Clusters 59

Fig. 2A. Molecular structure of LHFe 4(CO) 13 ] 0 0

(Manassero M, Longoni E, Sansoni M (1976) J . C C
Chem . Soc. Chem . Comm. 1976 :919] 0c co °c co

00 C'° oc co

(44
t:0
oC co
00 H H

o o
0
or
. co L 0 CO ~°
c c
0 0
clusters . Indeed no bridging CO groups have been observed in binary neutral a b c
carbonyl cluster M,„(CO)„ of the third-row metals . Only when the electron Fig. 2.5. Examples of the influence of cluster electron density on the bonding mode of CO in metal
density on the metal atoms is augmented through substitution of the CO by clusters. (a) Ir4(CO)i2 ; (b) [H 21r 4 (CO) 10 ] 2- ; (c)1r 4 (CO) 10 (PPh3 )2
better donor ligands or by development of formal negative charge, bridging CO
interactions are generated . Such an effect is exemplified by the structures of the
cluster species illustrated in Fig . 2.5 . As observed, the dissipation of electronic Table 2,1 . Ranges for internudear distances and stretching frequencies of carbon monoxide in metal
charge into the ligands appears to play an important role in the distribution of cluster carbonyls
the carbonyl ligands between terminal and bridging modes . Bridging carbonyl
C-O Group C-0 Distance (A) v(C-O) Frequency (cm - ' )
ligands are indeed better rr-acids and more effective in removing electron density
from the metal cluster than those bonded terminally . terminal 1 .12-1 .19 2150-1950 (1850)
The distinct bonding modes of CO-ligands appear to be associated with edge-bridging 1 .165-1 .20 1900-1750 (1650)
face-bridging 1 .19-1 .22 1800-1700(1600)
diAerent -acceptor capacities.,- That similarly to mononuclear carbonyl com
plexes, is reflected by the strength of the CO bond . Thus, as the metal-carbon ' In the presence of electron donors or negative charge lower frequency values are observed .
bonding changes from terminal to edge-bridging or to face-bridging an appreci-
Reference
able reduction of CO bond order is observed . Indeed carbon-oxygen bond
distances are in general longer for both types of bridging species -about 20 pm Chini P (1968) Inorg . Chim . Acta Rev . 2 :31
for edge-bridging and 40 pm for face-bridging carbonyls -than the distances
found for an equivalent terminal carbonyl . Frequency ranges for the stretching
band v(CO) in clusters are shown in Table 2 .1 . C
C C
Isocyanide .Isocyanide (RNC) are as ligand in transition metal complexes
electronically similar to carbon monoxide . Nevertheless they are in general
somewhat better donors than the carbonyl group . Terminal as well as three- a b C d e
center, edge-bridging bonding modes are known for isocyanides . Terminally
Fig. 2.6. Modes of bonding of alkenes in metal clusters
isocyanides show practically linear RNC arrays; however in the bridging mode,
bent RNC bonds are observed . Analogously to carbonyls, a reduction of the
RNC bond order is produced on going from a terminal to a multicenter bridging
bond. clusters . The simple conventional pit-dit bonding well known for monuclear
complexes is practically not observed in metal cluster complexes . The coordina-
Hydrocarbons. A variety of unsaturated hydrocarbons such as monoolefins, lion of olefincs to clusters normally occurs with formation of metal-carbon
linear and cyclic dimes, cyclic tetraenes etc . have been found and structurally bonds at the expense of olefin carbon-hydrogen bonds . Compounds with
characterized as ligands bonded to metal clusters . structures of type (a) and (b) in Fig. 2 .6 are normally termed I : 1 and 1 :2
The scheme in Fig. 2 .6 shows the modes of bonding more frequently ob- complexes respectively, denoting thus the the number of carbon atoms involved
served for the coordination of ethylene or other simple monoalkenes to metal in the o-bonding to cluster . Cyclic monoene compounds bear only species with


60 2 Transition Metal Cluster Chemistry 2 .2 Structural Characteristics of Molecular Metal Clusters 61

bonding mode (b) because mode (a) would imply a carbon-carbon bond rupture .
Figure 2 .7 illustrates the mode of bonding in other alkene systems . The bonding
patterns are equivalent to modes (a) and (b) mentioned above .
Similar to alkenes, the modes of bonding of alkynes in clusters is more (.Q
complex than in monuclear compounds . In metal clusters, alkyne carbon atoms
are normally bonded to two, three or four metal atoms . It is apparent that the
interaction with the metal atoms produces an extensive orbital rearrangement
Fig. 2.9. Schematic representation of the structure of
on the carbon centers . Carbon-carbon distances are in this process substantially Co,(CO), r,(C Z H,C = ('C 2 H,). [Dahl LF, Smith DL,
lengthened ; in some cases distances near to those of a single carbon-carbon (1962) J . Am . Chem. Soc. 84 .2450]
bond are observed . The scheme in Fig . 2 .8 shows basic structures for alkyne

cluster complexes . Mode (a) involves an interaction of the ligand with four metal
0 atoms leading to a butterfly array, and mode (b) or (c) with three metal atoms in
0 C c0
o c 0 t either a triangular cluster or a M 3 triangular face in a larger cluster . As can be
OC CO cc CO - • P seen in the structure of the complex Co,(CO) ta (C 2 H 5 C--CC 2 H 5) shown in
Fig . 2 .9 the alkyne complex is practically a six-atom dicarbo-metal cluster .
l
oc

r.
o Oc co oc CO

t Oc •~ 1l. oc ~"s+A co
• , 0 ! c
. C
0 o 2.2 Structural Characteristics of Molecular Metal Clusters
o b c

0 2 .2.1 Structural Techniques

C

Among the techniques more frequently used for elucidating cluster structures
are crystallographic studies by both single-crystal X-ray and neutron-diffraction
. techniques, multinuclear high resolution nuclear magnetic resonance INMR),
and infrared spectroscopy .
0c •~ • CO A great deal of the existing knowledge about structures, stereochemistry, and
precise structural parameters of molecular clusters have been obtained by single
d
crystal X-ray diffraction studies . To obtain adequate single crystals is the major
Fig. 2.7. Modes of bonding of some special alkcnes in metal clusters . (a) trans and (b) cis isomers of limiting factor for the application of this technique . Precise location of the
Os,(CO) 10 (C,H o ) : (c) Os 3 (CO),(PPh,),(C F H,I ; (d) Ni,(CO),ICF,CCCF,XC,H .I hydrogen atoms in hydride clusters often requires complementary neutron
diffraction studies . Although the potential precision of crystallographic deter-
minations is very high, it is not always accomplished because of disorder
problems, small or poor quality of the crystals . or limited data sets.
High resolution nuclear magnetic resonance is the most effective structural
technique for studies in solution . Although in some ideal cases, such studies can
define structure and stereochemistry, it is not possible to obtain structural
parameters by this method . Nuclear magnetic resonance techniques have
proved to be an excellent method for studying dynamic processes in clusters .
Infrared analysis is employed largely as a diagnostic technique which is very

X
R b c useful, for instance, in determining the coordination mode of the ligands .
Pis XL Structural information as the molecular symmetry cart be obtained by this
at Music structures of some alkyne cluster complexes . (a) Bonded to a butterfly array of metal
l lg to an octahedral M,C2 framework ; (b) and (c) isomeric forms of interaction with method only occasionally when the clusters have a relative high symmetry and
triangular fact the use of isotope-substitution techniques is possible .


62 2 Transition Metal Cluster Chemistry 2 .2 Structural Characteristics of Molecular Metal Clusters 63

2.2.2 Metal Cluster Geometries 2.2 .3 Trinuclear Metal Clusters

High symmetry is one of the principal characteristics of metal clusters . Gener- The number of cluster species with a triangular array of metal atoms which have
ally, metal atoms are arranged in the cluster defining regular polyhedra as been characterized by X-ray diffraction analysis is rather large . Low as well as
triangles, tetrahedra, octahedra etc . . Furthermore, polyhedra defined by the high-valence triangular clusters are known . The former are numerous and
metal positions in metal clusters arc largely deltahedra, i .e . polyhedra with all mostly carbonyl species ; the later are practically restricted to rhenium halides .
triangular faces . However, arrangements other than deltahedric such as square- Selected examples of triangular trinuclear metal clusters are described in Table
planar or nearly square-planar clusters, trigonal prismatic, or C,,-capped 2 .2 . In most cases the metal atoms in the cluster are equidistant, but there are
square-antiprism clusters are also represented though to a lower extent . The also many examples in which the internuclear distances are not equivalent .
majority of metal atom arrangements M,,, in clusters may be considered as
representing fragments of any close-packed array of metal atoms, hexagonal
close packing (hcp) or face centered cubic packed (ecp) . Thus, relatively common
cluster geometries such as triangle, tetrahedron, square-based pyramid, trigonal Table 22 Selected examples of trinuclear transition metal clusters
bipyramid, octahedron, etc. are formally fragments of a hcp array . Figure 2.10 Ref.
Compound Remarks
illustrate some geometries found in molecular cluster structures and their
relationship to close-packed arrays found in bulk metal . Nb 3 O, Three-dimensional infinite structure formed by I
3 .
cross linking of Nb triangles
[Nb3(p-C1))6(Cp')3]' Counterion chloride : Nb 3 triangle 2,3
symmetrically bridged by p 2 -0 atoms .
d(Nb-Nb) 3.334 A . With
tetracyano-p-quixo-dimethane (tenq) as
counterion, a dication with similar molecular
geometry is stabilized .
MID Nb 3 Cl 3 (p-Cl),(p 3 -0)(p 3 -X)(Cp*)3 X = ON, Cl . Triangular Nb 3 array in which one 4
edge has one short (2 .92 A) and two long
Nb-Nb distances (3 .28 and 3 .29 A) .
Nb(co1(p1-o)
363 -, (1-131 Distorted triangular Nb 3 unit. 5
ietrocapped
d (ND -Nbl = 3 .044-3 .320 A . Bridging CO
ligand is really a r) 2 -(p,-C, 13 2 -O) unit .
d(CO) = 1 .303 A.
C,
to
M 6 [M 3 (CO) a (p-CO)3 (p 3 -S)) 2- M = Cr. Mo and W (in Mo 2W) . Cluster core is 6
~,a I( a tetrahedral M 3S unit with p-CO ligands lying
~.p below M 3 plane .
Zn 2 Mo 3 O s Triangular Mo 3 units, d(Mo-Mo) = 2 .53 A . 7
octahedron
[Mo i{13 3 -CMe) 2 (p-O 2 CMe)s (H2 0)3 ] 2 ' Triangular Mo, units d(Mo-Mo) = 2 .814 8
Mo 3 (p-As)(p-O)3(Cp)3 Triangular array of Mo atoms 9
t d(Mo-Mo) = 2 .666-2 .809 A .
Triangular Mo, unit . d(Mo-Mo) = 2 .812 A .
vl~
- ~~ Mo3(p3-S)(p-S)2(Cp)3 10
M5
VALN M0 3(CO)6 (µ 3 -CF)(Cp) 3 Triangular array of Mo atoms . It
nido [W3(p3-Ol(1t-O)2F6]3- Equilateral triangular W 3 unit. 12
d(W-W) = 2 .515 A .
W(R)2 (p3 -O)(p-OR') 3 (OR')4 R = CH 2 Ph ; R' = 0-i-Pr. Triangular array of 13
W atoms. Both hydrocarbyl ligands are
M4 Oft equivalent.
,~ Mn 3 (~i,-NO)(p-NO) 3 (Cp) 3 Triangular Mn 3-unit . d(Mn-Mn) = 2 .506 A . it
Mn 3 (CO), 2 (CH 3 NNl Mn 3 bent configuration .132 16
a rachno terminal-diazo-nitrogen . Second nitrogen
coordinates the other Mn(CO) 4 fragment .
Fig . 2 .10. Some types of geometries frequently found in molecular cluster structures and their
d (Mn-Mn) = 2 .826 and 2 .807 A . Angle
relationship to the close-packed arrays found in bulk metals (arachno, nido and tetracapped Mn-Mn-Mn = 107.4 A .
denominations refer to fundamental octahedral geometry)
[Mn 3 (CO), 4 ] Linear Mn 3 unit (0 4,), d(Mn-Mn) = 2.895 A. 17

64 2 Transition Metal Cluster Chemistry
Table 2 .2. (continued)
Compound
Re3CI 9
[Rc 3 (p-CI) 3C1 9 ] 3-
Re 3 (p,-Cl) 3 (CH,SiMe3 ) e
Re 3 (p-Me) 3 (CH,Ph)6
Fe3 (p-CO)2 (CO),o
Fe 3(CO) 9 (p-CO) 2 PPh 3
Fe 3 (CO)9 (p3 -CO)(p 3-NSiMe3 )
[Fe,(CO) o (u-CO)(u 3 -CO) J 2 -
Fe3(CO)9(p3-S)2
Fe3 (CO) 9 (u3 -SM(CO 5 (p 3 -PBu')
Fe3(CO)6(p 3 -SC 6H 4NN) 2
Fe 3(p-CO)3 (p 3 -NO)(Cp') 3
Ru 3 (CO), 2
Ru3(CO)i2_,(CNBu`)„
Rus( CO)ho(p-NO 3 ) 2
Ru3(CO)6(u-CO) 3 [MeSi(PBu 2 ) 3 ]
Ru3(CO)8L4
Ru,(CO) 6 (u-CO)(C, oH s )
Ru3(CO),(C 5H 5 ) 2
[Ru3(PMe3 ) s (p-CH,).4 ] 2 '
2 .2 Structural Characteristics of Molecular Metal Clusters 65
Table 2.2. (continued)
Remarks Ref. Compound Remarks Ref,
Two dimensional polymeric sheets build by Re, 18 [Ru l (p3-OMe) 2 (Cp')3 ] - Triangular Ru 3 unit bridged symmetrically by 37
units held together by chloride bridges (Fig. two p-OMe groups . d(Ru-Ru) = 2 .958 A .
2 13a). d(Re-Re) = 2 .49 A . Os 3 (CO)32 Isostructural with Ru 3 (COI,2 (Fig. 2.lla) 38
Equilateral triangular Re 3 unit . Cl-bridges in 18 Os 3 (CO) 3 , { P(C6F,J 3 ) Os atoms form an approximate isosceles
Re 3 plane plane (Fig. 2 .13a). d(Re-Re) = 2 .47A . triangle, Phosphine ligand coordinated
Re 3 units. d(Re-Re) - 2 .387 A . 19 equatorially. d(Os-0s) = 2 .867-2.920 A .
20 Os 3 (CO)„(NCMe) Triangular array of Os atoms 39
d(Os-Os) = 2,829-2.951 A.
Slightly distorted isosceles triangle (Fig . 2 .1 IB) 21
Bridged edge (2 .558 A] shorter than the mean of Os 3 (CO)5 ICS)(u 3-S( 2 Os3 core form a wide "V" . One edge of the Os 3 40
the other two (2 .660 Al triangle is rather large (3 .642 A). u 3-S ligands
cap either side of the Os 3 triangle.
Replacement of equatorial CO by PPh 3 in 22 d(Os-Os) = 2 .780-2 .830Ak
Fe3(CO),2 . Asymmetry and d(Fe-Fe) is
retained . OS 3 1CO)„1 2 Sraight chain of Os atoms . Equatorial Iodine 41
atoms occupying trans positions to each other
Triangular hicapped Fe 3 unit. 23
on terminal Os atoms . d(Os-Os) = 2.93 A .
d(Fe-Fe) = 2 .535 A .
[Co 3 (CO)6 (p-CO)3(p3-CO)] - Co atoms form a regular triangle . 42
Triangular Fe y unit . d(Fe Fe} = ? .596 A . 24 d(Co-Co) = 2 .462-2.489 A .
Open Fe3 triangle . d(Fe-Fe) = 2 .58 and 2 .61 A . 25
Co3 (CO) 9(u 3-PPh) Triangular Co3 unit capped by the p 3 -PPh
M = Cr, W. Fe atoms define open triangle 26 ligand. d(Co-Co) = 2.717 A .
capped by both, p 3 -PR and u 3-SM(CO) s
({C03(CO)9(/'3_C)) 2 SCO) Two Co C(CO)Q units joined by aC(O)-S-chain 43
fragments. d(Fe-Fe) = 2 .65-2 .69A and 3 .49 A
(non bonding). d(Co-Co) = 2 .480-2.472 A .
Three Fe atoms form a linear cluster . Each Co 3 (CO) 5 (p-PCy 2 ) 3 Cy = Cyclohexyl . Co 3 triangle. The three 44
27 phosphido groups lie above, in, and below the
heteroatom . S and N, bridges two Fe-atoms but
not the same pair. d(Fe-Fe) = 2 .494 A• Co 3 plane . d (Co-Co) = 2 .57 A .
Triangular array of Fe atoms . Co 3 (p-CO)2 4u 3 -CO)(Cp) 3 Triangular Co3 unit . 45
28 d (Co-Co) = 2 .438-2.529 A .
d(Fe-Fe) = 2 .533 A
[Co3(p3-X)(u3-Y)(Cp)]° * X = Co, Y = S n = 0; d(Co-Co) = 2 .452 A . 46
All carbonyl groups are terminal (Fig. 2 .lla). 29 X = Y = S, n = 0; av. d(Co-Co) = 2 .687 A .
d(Ru-Ru) = 2 .854 A
n = 1 ; d (Co-Co): two long (2.649) and one short
n - 1,2. Triangular Ru 3 unit . 30 (2.474 A) distances .
d(Ru-Ru) = 2 .847-2866 . A.
C0 3 (p 3 -fl'-CS) (N3-S) (Cp) 3 Triangular array of Co atoms with a triple 47
Open triangle Ru 3 . Di-bridged Ru-Ru is non 31 bridging thiocarbonyl ligand .
bonding (3.15 A) . d(Ru-Ru) = 2.866 A . d(Co-Co) = 2.43 A .
Equilateral triangular Ru, unit . 32 i Rh 3 (CO) 6 (PPh,H)(p-PPh 2 ) 3 Triangular array of Rh atoms . However 48
d (Ru-Ru) = 2.917 . Silyl group lies above Ru3 internuclear distances
plane bonded with one P atom to each metal [d(Rh-Rh) = 3 .130-3.24 A] imply negligible
atom . metalmetal
- bonding interactions. Metal and
L = PMe 2 Ph and P(OR) 3 (R = Me, Et, Ph) . phosphor atoms form a near planar six-member
33
Non-carbonyl ligands occupy equatorial Ph 3 P 3 ring,
positions in Ru 3 triangle . [Rh 3 (CO) 5 (u 3-PMe)(PMe 3 )3 ]* Equilateral Rh 3 triangle capped, at most, 49
d(Ru-Ru) = 2 .740 (bridged) and 2.944 34 symmetrically . This species is part of the
(unbridged) azulene coordinate to one Ru atom compound FeRh a (CO), o (PMe) (PMe3 ) s
through a five-member ring, and to the other formed by this cation and the anion
two through the seven-member ring . [FeRh 5 (CO) 13 (PMe 3 )] - .
Isosceles triangle of Ru atoms . 35 Rh 3 lCO)s (p-PPh2 ) 3 Triangular array of Rh atoms . 50
d(Ru-Ru) = 2 .938 and 2.782 A each d(Rh-Rh) = 2 .698-2 .806 A .
cyclo-octatetraene is bonded to a pair Ru Rh 3 (p-CO) 3 4Cp)3 Equilateral triangular unit . d(Rh-Rh) = 2.62 A . 51
atoms. ) isomorphous
There o other isomerCwhich
2(1
Linear arrangement of Ru atoms linked by 36 llp- (J ~ )( F 3•
bridging methylene groups and Ru-Ru bonds fr3 (CO) 6 (Ph)(u-dppm) (p 3 -PPh) Triangular array of Ir atoms . 52
(2 .637 A) d (Ir-Ir) = 2.768-2 .779 A .


66 2TransitoMelCurhmisty 2 .2StrucalCh eistcofMluaretCs 67

Table 2.2,(contiued) Table 2.2.(contiued)

Compound Remarks Ref . 16HermanWA,ZiglMLednhamrK(197)Angew .Chem . Int . Edn. 15 :368
TriangulI a-unit 17BauR,KirtleySWo TN,inarkS(1974)J . Am .Chem . Soc. 96 :998
Ir 3 (CO)3(Cp)3 .d(Ir-i)=2 .6693-2.876 A . 53 18CotnFA,MagueJT(1964)Inorg .Chem . 3 :1403 and 3 :1094
Ni 3 (u 3 -CO)2 (Cp)3 TriangulN 3 unit .d(Ni-)=2 .530. 54 19Hursthoe MB, MalikKA(1978)J .Chem . Soc., Dalton Trans ., 1334
Ni,(k3-CEt)p Triangul yofNatms . 55 2018/3WongAC,EdwarsPGWilkno,RevaiMHurthoseB(198)J,Chm .
d(Ni-)=2 .325-2 .349 A . Soc., Dalton Trans., 219
3 (u3 -S) 2 (Cp)3 21 Cotton FA, Troup JM (1974) J . Am.Chem . Soc. 96 :4155
Ni Equilater ng Ni 3 unit . 56 22 Raper G, McDonald WS (1971) J .Chem . Soc. (A) 3430
d(Ni-)=2 .80 A.
23BarnetL,KugC(197)Anewhm . 83 :969
Ni 3 (u-NCBu`)(Cp)3 IregulaNi 3 triangle .d(Ni-)rangfom 57 24LoFYK,ngiGChPLowerD,ahlF(1980)J .Am,Che . Soc. 102 :7691
2.334 to 2 .386 A . 25WeiCH,DahlLF(1965)Inorg .Chem . 4 :493
Pd 3 (CO)2 (µ-t-Bu2P)3Cl TriangleofPdtms . Two atoms bear 58 26WinterA,ZsolaLHutnerG(1983)J .Organumet .Chem . 250 :409
aterminlCOgoupwhetirdsbon 27 Pannell KH, Mayr AJ, van Derveer DU (1983) J . Am .Chem . Soc . 105 :6186
toaCl-ignd . d(Pd-Pd) = 2 .975 A. 28MulerJ,Son1AkhuT(98)J .Organomet .Chem . 367 :133
[Pd3 (PEt 3 )3 (p-Ph 2 ) 2 (p-CI)]' Isosceles Pd 3 unit 29ChurcilMR,HoanderFJutchisoP(197)Inrg .Chem . 16 :2655
. d(Pd-Pd) = 2 .93(twice),
2 .89 A . Cl-igandsbrhotedg 30BruceMI,atisonJGWlRC,PatrickJMSelonBW,hitAH(1983)J .Chem . Soc.,
. Dalton Trans., 2365
Pt3(,u-CO)3[P(CeHtj)3]a Slightydsore cltiange . 59 31NortnJ,Clma DoetiG,RbnsWT(1972)Iorg .Chem . 11 :382
d (Pt-Pt) = 2 .675, 2736 and 2.714 A . 32 de Boer JJ, van Doom JA, Masters C (1978) J .Chem . Soc .,Chem . Commun ., 1005
P1 3 (ButNC)6 Equilater ng P 3 unit . 60 3BruceMI,LidlJBnShawktly0,ea1SkltonBW,hieAH(198)J .
d(Pt-Pt) = 2 .531 A . Organomet .Chem . 369 :217
Pt3(PEt 3 )4 (PhC 2 Ph) 2 V-shapedrngPt-oms 34ChurcilMR,SoeFWrmaldJ(197) .Organomet .Chem . 28 :C21
. 61
d(Pt-Pt) = 2.905 A; anglePt- =14' 35BentMJ,Co FALegzdinsP(1968)J . Am.Chem . Soc. 90 :6335
36JonesRA,Wilk GasAMR,HurthocBMalikKA(1980)J .Chem . Soc., Dalton
[Cu3(u3-q'-C CPh)(p-dm 3] 2 ' Triangul yofCatms . d(Cu-Cu) : two 62 Trans ., 171
short(2 .817 and 2 .904 A) andoelrg 37KoleU,sakwiJBoeR(198)J .Organomet .Chem . 378 :449
(3 .274 A) distanceug lib 38ChurcilMR .DelorBG(197)Ing .Chem . 16 :878
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[Au3(u-(CH 2 ) 2 Ph 2 )4 ]' ChainofAutms pirocyl 63 Dalton Trans., 233
arngemtofwdiaurphscyle 40BroadhustPV,JnBFGLewisJ,RathbyP(1980)J .Organomet .Chem . 194 : C35
[Au 2 ((CH 2 ) 2 Ph 2 ) 2 ] orientda90'liveto 41 Cook N, Smart L, Woodward P (1977) J .Chem . Soc., Dalton Trans ., 1744
eachotr . d(Au-Au) = 3.050 A . 42AdamsHN,FchinetGSralJ(1980)Angew .Chem ., 1nt, Edn . 19 :404
[Au3(p-CPMe 3 ) (PPh 3 ) 3 ]+ 43Gervasio,Rt SangheliPL,BrG(1983) .Chem . Soc., Dalton Trans., 1613
TriangleofAutmswhicarebou 64
equidstanfromc Cat . 4AlbrightT,KanSAfMBrdJ,onesRALladJK,SchwbT(198)Inorg .
Chem . 27 :1246
d(Au-Au) = 3 .18 A.
45BaileyWI,CotnFAJamersD,KolthmerBWS(1982)Inog .Chem . 21 :3131
46FrischPD,alL(1972)J . Am.Chem . Soc . 94 :5082
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52HardingM,NcholsBSmitAK(1983)J .Chem . Soc ., Dalton Trans., 1479
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5HermanWA,BisckHZeglrML,WidnhameKSglR,hderD(198)J . Am . 54MajJ,ReADhlLF(1982)J . Am.Chem . Soc. 104 :3054
Chem . Soc . 103 :1692
5LehmkulH,KrgCPasynkiewzS,oplasJ(198)Organomeltics7 :2038
6DarensbougJ,ZldeDSanchzKM,elordT(198)Ing .Chem . 27 :821 56VahrenkmpH,UctVADahlLF(1968)J . Am .Chem . Soc. 90 :3272
7 McCarroll WH, Katz L, Ward R (1957) J . Am .Chem . Soc. 79 :5410 57KamijyoN,WtnbeT(1974)Bul .Chem,Soc . Japan, 47 :373
8ArdonM,Bi . Cotton FA, DoriZ, KaftoryM,lhnueBWSKapoM,ReisnrG
(198)Inorg 58ArifM,HeatonDEJsRA,NunCM(1987)Iorg .Chem . 26 :4228
.Chem . 20 :4083 59Abinat,CruGMscoA(1976)Inrg .Chim . Acta 16 : L3
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10VergaminPJ,hkpHDalLF(197)J . Am.Chem . Soc . 93 :6327 1509
1SchulzeM,Hart]SpelK(1987)J .Organote .Chem . 319 :77 61BoagNM,GrenHowadJAK,SpencrLtasfildRFD,SoneGAThmasMDO,
12MenmaK,tsR(1976)Angew .Chem . Int . Edn. 15 :118
13 Chisolm VicentJ,WodwarP(197)J .Chem . Soc .,Chem . Commun ., 930
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14HohmanVM,Krut-SieglLWdnhamrK,SculzeWZigrML(198) .Anorg . 378 :C11
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2 Transition Metal Cluster Chemistry 2 .2 Structural Characteristics of Molecular Metal Clusters 69

68

CI
Carbonyl Metal Clusters . The equivalence of metal atoms in the clusters and
Cl S i ct
thus the symmetry of the arrangement is determined by the distribution of the _ci Ct Cl
carbonyl ligands between the terminal and bridging modes discussed above . In
the compounds Os 3 (CO) 12 and Ru 3 (CO) 12 (Fig . 2.l la) with all carbonyl CI CI- f CI
Cl ci
groups as terminal ligands metal atoms form an equilateral triangle . However, CI
in the equivalent iron compound, Fe 3 (CO) 12 (Fig. 2 .llb), there are both ter- CI Cl y pct
1\ l C1
minal and bridges carbonyl groups . The asymmetric distribution of carbonyl C I--
groups leads in this case to non-equivalent iron atoms so forming an isosceles a b
triangle . There the Fe-Fe distances between CO-bridged iron atoms are shorter
Fig. 2.12. Schematic structures of (a) Rhenium (Ili) chloride and (b) the anion [Re 3 CI, 2 ]' -
than those to the vertex with all terminal carbonyl groups .
There are numerous triangular metal complexes containing hydrogen . Struc-
tural features of hydride metal clusters will be separately described in Chapter 3 .
The study of cluster hydrides is of considerable interest since, as it will be CH 3 0
S I
discussed later in this Chapter (Sect . 2 .6), they are intimately associated with C
-I&
0
important catalytic processes e.g. Fischer Troppch processes for ammonia and Fe (c0) 3 \ . F\
methane synthesis .
Many non-carbonyl ligands such as NO, S, PR, 0 or RC can be edge or (CO) 3

face-bridging ligands in triangular metal clusters (Fig . 2 .12) . Phosphines PR 3 are 1

Fe(CO) 3 (CO) 3R
typical donor terminal ligands in trinuclear triangular clusters .
S /

a b c
High-Valence Trinuclear Rhenium Clusters . Trinuclear rhenium arrangements
with triangular geometries are stabilized by n-donor ligands as being the halide Fig. 2 .13. Examples of structures of triangular metal clusters containing main-group bridging
ions . The X-ray diffraction analysis of rhenium(lll) chloride shows that the ligands
compound is not a simple ionic compound but a polymer built up by [Re 3 Cl 9 ]
units bonded by chloride bridges (Fig . 2 .13a) . The same type of structure with
three edge-bridging chlorides and three terminal ligands has the substituted
monomeric species Re 1 C:I,,L 3 (Fig . 2 .13b). As it can be observed from data in 2 .2.4 Tetranuclear Metal Clusters
Table 2.2, the intennetallic distances in these rhenium clusters are about 2 .48 A,
i .e . ca 0.27 A shorter than in the metal (2 .75 A) and significantly shorter than Selected examples of tetranuclear clusters are described in Table 2 .3.
those expected for simple Re-Re bonds . This feature is interpreted in terms of Many of the known tetranuclear clusters show a tetrahedral arrangement of
double bonds between the metal atoms and explained, as it will be seen in the metal atoms with six metal-metal bonds . However, there are also other geomet-
next section, by considering the number of electrons disposable for building the ries. For instance, the type of structure observed for the compound Ru 4 (CO) t 1
cluster structure . (p4-C 8 H 10 ) illustrated in Fig. 2 .14a known as "butterfly" structures and which
can he formally considered to result from the rupture of one of the tetrahedral
metal-metal bonds . The interplanar dihedral angles in butterfly arrangements
are not always small ; there are indeed examples of practically planar butterfly
0 0
c °~ c
""Co o
0
c
0
c structures as occurs for instance in the anion [Re,(CO)16]'- (Fig. 2 .14b) .
-co jca Square-planar arrangement of the metal atoms, as that observed for the clusters
ocj
0
0C11 l
° Mo 4 (OPi,)8CI 4 and Fe4(CO) 11 (NEt)(ONEt) (Fig. 2 .15), are also possible for
oc-' tetranuclear clusters. Energy differences between butterfly and tetrahedral metal
° c 1co
c 1
/ ; co o i arrangements appear to be relatively small, thus dynamic rearrangement of the
c
0
oC former through tetrahedral geometry is often possible.
0 0 0 Among tetrahedral metal clusters the carbonyl complexes are the more
Fig . 2.11 . Schematic representation of the
structures of dodecarbonyls of group
representative . Neutral carbonyl clusters of cobalt and rhodium have similar
a b 8 metals (a) Ru, Os ; (b) Fe structures (Fig. 2 .16) with nine terminal and three edge-bridging carbonyl


70 2 Transition Metal Cluster Chemistry 2.2 Structural Characteristics of Molecular Metal Clusters 71

Table 2.3. Selected examples of tetranuclear metal clusters Table 2.3. (continued)

Compounds Remarks Ref. Compounds Remarks Ref.

Ti4(al'-7 sC,H4)(gs-q s-C1oH8)(p3-N21(Cp)5
Ti4 (MeCsH4)(p3-S) 4
V4(MeC5H 4)(p 3-S)4
Cr4(p3-S)2(p3 - L)2(CP)4
Cr4()Us-O)4(Cp)4
[Re,(CO) 1 6] 3-
[Re4(p3-X)4(CN)12]`
[Fe4(CO)9(p-CO)3(p 3-CO)] 2-
Fe4(CO) 1 2(i-CO)(p 4 -C)
[Fe4(CO) 12(p-CI}2-
[Fe4(CO)1 3 (N 4-CCO 2 Me)] -
Fe4(CO)12(p3-n 2-CS)()j 3-S)
Fe4(CO) 10 (p-CO)(p 4 -pR)2
Fe,(CO)10(p-CO)(p,-P(tol-p)) 2
Fe4(CO)s(Py)4
Ru4(CO) 12(P-CO)(p-Cl)
[Ti2CP2(7` - i 5 C,0HaI(p3-N2)[Ti3CP 3
(q'-nS-CsH4)] ; v(N - N) = 1282cm - '
Cubanc cluster: Interpenetrated tetrahedra of
S and Ti atoms where the latter are bonded to
terminal ligands . Two sets of d(Ti-Ti), 3 .00
(four) and 2 .93 A (two).
Interpenetrated tetrahedra of S and V atoms
(cubanc cluster). d(V-V) - 2.873 A (av . two
slightly different sets of distances).
Cubane-like structures ; L = CO, S.
Cr atoms form an approximate tetrahedron
capped by the Cp rings and by the O-atoms
above each face . d(Cr-Cr) = 1 .937A .
Re-atoms define a parallelogram with Rc-Re
bond across the shortest diagonal . d(Re-Rc)
2.596 2,96k
X = S or Se. d(Re-Re) = 2 .755(S) or
2.805(Se) A .
Tetrahedral Fe4 configuration . Apical
Fe(CO) 3 group is symmetrically bonded
(258 A) to the basis Fe 3(C0)R(p-CO) 3 (p 3 -CO)
[d(Fe-Fe) = 150A] .
Fe atoms in a butterfly configuration (dihedral
angle ). d(Fe-Fe)
101-- 2 "642
.545-2 . I
A each of the other two
Butterfly arrangement of Fe atoms (dihedral
angle 102 .4') with C atom bridging the central
Fe-Fe bond . d(Fe-Fe) = 2-533-2 .637A .
Fe4 unit with butterfly configuration (dihedral
angle 130'1 . d(Fe-Fe) = 2 .430-2 .489 A .
Three Fe atoms define an equilateral triangle;
the fourth is terminally bonded to the triangle .
CS-group is terminally bonded to Fe(4) via
sulfur . The C atom is capping the Fe 3 triangle.
d(Fe-Fe) = 2.564 ( a v . i n the triangle) and
2.710 A .
R p-tolyl . Fe-atoms define a quadrilateral
bicapped by the p4 -PR groups. d(Fe -Fe): three
ca . 2 .69 A and one shorter 12 .42 A) assigned to
one double bond .
Fe and P atoms define the vertices of
a distorted octahedron with PR-groups in
axial positions. One CO-group is bridging an
equatorial Fe-Fc hand (2 .44 A). d(Fe-Fe) _
2.69 A
Fe atoms define the vertices of a rhombus . Fe
atoms on the shortest diagonal are each linked
to 2 pyridine groups . d(Fe-Fe) = 2 .55 A .
Butterfly arrangement of Ru atoms with a Cl
atom bridging the two wing-type metal atoms .
p-CO group is bridging central Ru-Ru bond .
d(Ru-Ru) = 2_832 A .
Ru 4(('O) 12(C 2 Ph2) Butterfly Ru 4 configuration capped by the 17
I
PhCCPh group . d(Ru Rut = 2 .73-2 .85 A .
2 Ru a(CO) 31 (p 4 -PPh)(p4 -n4-C6 H 4 ) Square Ru 4 unit capped on one side by 18
a p 4-phosphinidene ligand and, on the other,
by the benzene (vrtho-dimetallated benzene) .
d(Ru-Ru) = 2 .791-2.943 A .
2,3 Ru 4 1C0)„(PhC 2 Ph)(p-NPh) Pentagonal hipyramide with equatorial plane 19
containing two Ru atoms, two acetylene
residues, and the nitrene atom . This plane
is capped by two Ru(CO) 2 units with two
4
edge-bridging CO groups . d(Ru-Ru)
3, 5 - 2 .7-2.8 A .
Ru 4 (CO),,(p,-CI)2(p3-OEt) 2 Ru-atoms adopt a planar geometry that can 20
be described as two triangles sharing
6 a common elongated edge. Unshared edges of
one of the triangles are bridged by chlorine
atoms . The same triangle is capped on either
7 side by the oxygen atoms of the two ethoxy
groups .
8 Ru4(C0)5{P(OMe)3}(u3-C5H4)2(CP)2 Ru4 chain which can be considered as two Ru2 21
units (2 .760 A) jointed by the central, longer
(2 .887 A) Ru-Ru bond . Terminal Ru atoms
each with a Cp-ligand . The other C 5 rings are
9 bridging three Ru atoms, n 5 to one and )1' to
two .
10 Os4(C0)n(PMe,I n = 13, 14, 1S . n = IS: Os(CO)4 (PMe 3 ) acts as 22
a ligand to an 0s 3 (CO) 1 1 fragment. n = 14
planar Os, skeleton with two adjacent short
Os-Os (2 .779-2.784 A) and two long
11 (2 .982 3 .013 A), n = 13 tetrahedral framework
(d(Os-Os) = 2 .765-2 .869 A).
12 0s4(CO) 12 )p 3- NMe) Os atoms define distorted tetrahedron capped 23
by the N-atom of methylnitrene group on the
face containing three longer Os Os distances
(2.834 A) d(Os Os) = 2 .75-2 .835A .
Os 4(CO) 1 2(p-q 2-C 2 H 2 ) Os atoms adopt a butterfly configurations. 24
Three terminal CO-groups are bonded to each
13 metal . The acetylenic ligand lies over the
butterfly .
Os 4 (CO) 12(p 3 -S) 2 Butterfly Os, unit with sulfido ligands 25
bridging the two open triangular faces,
14 d(Os-Os): two long (3 .002-3.091 A) and three
short (2 .914-2.940 A) distances .
0s 4(CO) 17(p 3 -HC 2 Phl(p 3 -S) Butterfly Os ., unit with triply bridging sulfido 26
and alkyne ligands on the two open triangular
faces . d(Os-Os) = 2 .904 3 .083 A .
15
Os 4(C0) 1 ,L(µ 3-S) L = PMe 2 Ph, CN-t-Bu . Butterfly array of Os 27
atoms with p 3-S groups on the two open
triangular faces . L replaces a CO-group in
16 a wing-type Os atom d(Os-Os) = 2 .987
(L = PMe,Ph).

72 2 Transition Metal Cluster Chemistry
Table 2,3. (continued)
Compounds
Co 4(CO)y (p-CO) 3
[Co(CO)8 j+2-CO),1]-
COACO)10(p2 - CO)(JL4-GCMe)2
Co4 (CO) 1 ,(FIC 2 Et)
Co4(CO)„(k 2-CO) 2 (pe4-PPh 2) 2
Co4 (CO),(p-CO)3{P(OMe) 3 )2
Co 4(CO)4lµ-CO)(p 3-CO)2(Cp)2
Co4 (NO),(pt 3 -NCMe 3 )4
Co 4(PPh)(B 2 H 2 )(Cp),
Rh 4(CO)„(p-CO)3
Rh 4(CO)4(p 2 -CO)4 {P(OEt) 3 } ( tripod)
Rh 4(CO) 5(p 2 -CO) 3 [P(OPh)3 ] 4
[Rh4 (CO) 5 (p -PPh 2) 5 ] -
Rh 4 f-CO)4 {P(OPh) 3 }4(!r-SO 2 ) 3
[Rh 4 (CN(CH 2 ) 3 NC) 4C1 2 ]`'
1r4(CO) 12
Remarks
Apical Co(CO) 3 group is bonded to basal
CO 3 (CO) 6 (ji-CO), fragment .
d(Co-Co) = 2 .457-2 .527 A .
Tetrahedral Co 4 uni( . N-CO ligands define the 29
basal triangle. Iodine is terminally bonded to
apical metal atom . d(Co Co) = 2.493 A .
Co and Ce atoms define a irregular square
bipyramidal structure with Ge atom in apical
positions. d(Co-Co) = 2 .58 A (bridged) and
2.692-2 .721 A .
Butterfly Co o configuration . Dihedral angle
118 d(Co-Co) = 2 .55 A .
Rectangular Coo configuration; longer edges
are unbndged . d(Co-Co) = 2 .519 and 2 .697 A .
Co atoms define a tetrahedron bridged on
three edges by CO-groups (C 3 ,).
d(Co-Co) = 2 .523-2 .542 (eq-ax) and
2 .468-2.491 A (eq-eq).
Co atoms are forming a distorted tetrahedron . 34
d(Co Co) = 2.417-2 .494 A .
Distorted tetrahedral Co o configuration .
Isocyanide groups are capping the four
tetrahedron faces.
Pentagonal bipyramid containing four Co,
one P, and two B atoms in cluster core . Axial
positions occupied by Co atoms. Cp ligands
on metal atoms . d(Co-Co) = 2 .517-2.521 A .
Isostructural with Co4(CO) 12 (vide supra).
d(Rh-Rh) = 2 .70-2.80 A .
tripod = HC[P(CeH512j3 . Distorted
tetrahedral Rh4 array with three P atoms of
the tripod-ligand bonded in axial positions .
Each edge of basal triangle and one axial-
equatorial edge are bridged by CO groups .
Phosphorus ligand replaces terminal CO-
groups in Rh 4 (CO) 1i . d(Rh-Rh) = 2 .72 A .
Rh atoms define an arachnn or butterfly
structure that contains only PPh groups as
bridging ligands.
Rh atoms arranged in a butterfly structure
with a relatively small dihedral angle (82 .4°).
One SO, ligand is bridging the wing-type
metal atoms. The other two are bridging the
central metal-metal bond .
d(Rh Rh) = 2 .711-2 .78_2 A.
Linear arrangement of Rh atoms mode up of 42
two [Rh 2(LL)4 J 3 * Units
[d(Ru Ru) = 2.926,k] linked by Rh-Rh bond
12 .475,k)-
Tetrahedral Ir4 unit . d(Ir-Ir) = 2.293 A .
2 .2 Structural Characteristics of Molecular Metal Clusters 73
Table 2.3. (continued)
Ref. Compounds Remarks Ref.
28 [!r,(COl l ll+-C'O),BrJ - Structurally similar to Co,(CO) 12 (vide supra) . 44
One basal, terminal CO-group is replaced by
bromine . d(Ir-Ir) = 2.695-2 .745 (basal) and
2.696 A (apical) .
Ir4(CO) y p2,-(PPh 2 )3 (:H) IT atoms define the vertices of a tetrahedron 45
with the tripod-P-ligand capping a face.
CO-groups are terminally bonded .
30
dl Ir-Ir) = 2.684-2.695 A .
lr4(CO)5(}r-CO)3 (PMe 3 ) Metal tetrahedron displays a trigonal 46
pyramidal distortion with average apical and
31 basal edges of 2.747 and 2,894 A respectively .
Ir4(CO)3(dppm1, 47
32 Ir 4(CO) 2 tpr-COI 2 1p-AsBu,)4 Planar, rhomboidal IT, unit. Short axis 48
(2 .592 A) is consistent with an Ir-Ir double
33 bond . d(Ir-lr) around the outer edges of IT,
parallelogram: 2 .807-2.866 A .
Ni 4(N 2CO),,{P(CH 3 CH 2CN) 3 } 4 Tetrahedral Ni, unit, d(Ni-Ni) = 2 .51 A . 49
Ni 4(CO)4(CF 3 C,CF 3)3 Tetrahedral Ni, unit . CF 3 C 2CF 3 groups are 50
coordinated to three triangular faces .
d(Ni-Ni) = 2.378 (basal) and 2.660 A (apical) .
35 Pd 4(pr-CO) R (PBu 3 ) 4 Tetrahedral arrangement of Pd atoms with 51
CO ligands symmetrically bridged .
d(Pd-Pd) = 2 .778-2 .817 A .
36 Pd 4(p 4 -CO) 4 (OACL](AcOH) 2 Distorted square planar Pd 4 unit . Two short 52
(2 .663 A) and two long 12 .909 A) Pd Pd
distances. Pd-Pd-Pd angles differ from 90 - .
Square planar Pt, geometry . 53
Pt 4(pe-COOCH 3),1
37 d(Pt-Pt) = 2 .492-2 .498 A.
Pt 4 (k2-CO) 2 (ji g -dppm) 3 {Ph 2 P('H 2 P(O)(Ph2 )}Butterfly arrangement of Pt atoms (dihedral 54
38 angle 83 .7'). The five edges are bridged by CO
and dppm ligands . d(Pt Ptl = 2 .611-2.739 A .
Cu4 (MeN 5 Me)4 Cu atoms define parellelogram with angles 55
67' and 113' . d(Cu-Cu) = 2.64 A.
39
References
40
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74 2 Transition Metal Cluster Chemistry 75

2 .2 Structural Characteristics of Molecular Metal Clusters
I
Table 23 . (continued)

13 Vahrenkamp H, Wolters D (1982) J . Organomet. Chem, 224 :C17 ~. 0 0 0

14 Vahrenkamp H, Wucherer EJ, Wolters D (2983) Chem . Ber. 116 :1219
OC :: 0C C\ ~C
15 Fachinetti G, Fochi G, Funaioli T, Zanazzi PF (1987) J . Chem . Soc., Chem . Commun . 89 CO CO
16 Steinmetz GR, Harley D, Geoffroy GL (1980) Inorg . Chem . 19 :2985 I I CO
17 Johnson BFG, Lewis J, Reichert BE, Schorpp KT, Sheldrick GM (1977) J . Chem. Soc., Dalton OCR CO OC R 0 AC
Oc
Trans . 1417 / 0.C/ I C '-CO
18 Knox SAR, Lloyd BR, Orpen AG, Vinas JM, Weber M (1987) J . Chem. See., Chem . Commun . 0
1498
oc OC CO o cr 1~1c
Oc \C 0 C 0
19 Rheingold AL, Staley DL, Han SH, Geoffrey GL (1988) Acta Cristallogr . C44 :570 0 0
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a b
321 :409
21 Feasey ND, Forrow NJ, Hogarth G, Knox SAR, MacPherson KA, Morris MJ, Orpen AG (1984) 2-
J . Organomet . Chem . 267 :C41 Fig. 114. Structures type "butterfly" (a) Ru,(CO)„(µ4-C8"10) (b) [Re 4(CO) 16]
22 Martin IR, Einstein FWB, Pomeroy RK (1988) Organometallics 7 :294
23 Lin YC, Knobler CB, Kaesz HD, (1981) J . Organomet. Chem . 213 :C41
24 Jackson R, Johnson BFG, Lewis J, Raithby PR, Sankey SW(1980)J . Organomet . Chem. 193 : C1
25 Adams RD, Yang LW (1982) J . Am. Chem . Soc. 104 :4115
26 Adams RD, Wang S (1987) J . Am . Chem. Soc. 109 :924 R
27 Adams RD, Horvath IT, Natarajan K, (1984) Organometallics 3 :1540
28 Carve FH, Cotton FA, Frenz BA (1976) Inorg . Chem, 15 :380 Cl •R CI R
29 Albano VG, Braga D, Longoni G, Campanella S, Cerriotti A, Chini P (1980) J . Chem . Soc ., N
Dalton Trans. 1820 R R /-
30 Foster SP, MacKay KM, Nicholson BK (1982) J . Chem . Sac., Chem. Commun. 1156 ~• OC - / -Fe
31 Dahl LF, Smith DL (1962) J . Am. Chem . Soc. 84 : 2450 •
32 Ryan RC, Dahl LF (1975) J . Am. Chem . Soc . 97 :6904 R '/ ~0
33 Darensbourg DI, Incorvia MJ (1981) Inorg. Chem. 20 :1911
Fig. 2.15 . Cluster with square-
34 Altbach MI, Fronczek FR, Butler IG (1987) Acta Crystallogr . C43 :2283 CS \~ 0 / 1
Cl N -0 planar geometries . Schematic
35 Gall RS, Connelly NG, Dahl LF (1974) J . Am . Chem. Soc. 96 :4017
36 Feilong J, Fehlner T, Rheingold AL (1987) J . Chem. Soc. Chem. Commun . 1393 I molecular structures of (a)
R R Mo4(OP :) 5 Cl4 and (b)
37 Wei CH (1969) Inorg, Chem. 8 :2384
38 Kennedy JR, Selz P, Rheingold AL, Trogler WC, Basolo F (1989) J . Am. Chem . Soc., 121 : 3615 a b Fe4(CO) 11 (NEt)(ONEt)
39 Albano VG, Ciani G, Martinengo S, Chini P, Giovdano G (1975) J . Organomet . Chem. 88 : 381
40 Kreter PE, Meek DW, Christoph GG (1980)1 . Organomet. Chem . 188 : C27
41 Briant CE, Theubald BRC, Mingos DMP (1981) J . Chem . Soc ., Chem . Commun. 963
42 Mann KR, DiPierro MJ, Gill TP (1980) J . Am . Chem. Soc., 102 :3965
43 Churchill MR, Hutchinson JP (1978) Inorg. Chem . 17 :3528
44 Chini P, Ciani G . Garlaschelli L, Manassero M, Martinengo S, Sironi A, Canziani F (1978)
J. Organomet. Chem, 152 :C35
45 Cluca .s JA, Harding MM, Nicholls BS, Smith AK (1984) J . Chem. Sec ., Chem . Commun. 319
46 DeMartin F, Manassero M, Sansoni M, Garlaschelli L, Sartorelli. U(1981)J Organomet . Chem.
204 :C10
47 Harding MM, Nicholls BS, Smith AK (1984) Acta Crystallogr . 040 :790
48 Arif AM, Jones RA, Schwab ST, Whittlesey BR (1986) J . Am . Chem. Soc . 108 :1703 oc ca
49 Bennett MJ, Cotton FA . Winquist BHC (1967) J . Am. Chem . Soc . 89 :5366
50 Davidson JL, Green M, Stone FGA, Welch AJ (1975) J . Am . Chem. Soc. 97 :7490 ea
51 Moiseev II, Stromnova TA, Vargafting MN, Maze GJ, Kuzmina LG, Struchkov YT (1978) OC C CO Fig . 2.16, Schematic molecular structures of the
J . Chem. Soc., Chem . Commun. 27 0 dodccacarbonyls of cobalt and rhodium
52 Bogdanovic B, Goddard R, Rubach M (1989) Acta Crystallogr . 045 :1511
53 Carrondo MAAF de CT, Skapski AC (1978) Acta Cryst . B34 :1857
S4 Frew AA, Hill RH, Manojlovic-Muir L, Muir KW, Puddephatt RJ (1982) J . Chem . Soc., Chem.
Commun . 198
55 O'Connor JE, Janusonis GA, Corey ER (1968) J . Chem. Soc ., Chem . Commun . 445
groups . The analogous compound of iridium shows indeed only terminal CO-
ligands leading to a very symmetric structure . As discussed above, tetrairidium
clusters with bridging CO-ligands are observed only in compounds as
[H 2 lr4 (CO) to]' - and Ir4 (CO)1 10 (PPh 3 ) 2 (see Fig. 2.5) where a charge excess
in metal is induced.


2 Transition Metal Cluster Chemistry 2 .2 Structural Characteristics of Molecular Metal Clusters 77

76

Table 2 .4- (continued)

2.2.5 Pentanuclear Metal Clusters
Compounds Remarks Rcf
The number of possible geometric arrays of the atoms in the metal skeleton
increases with increasing cluster nuclearity . Thus, for pentanuclear clusters, Ru s(CO), s (p 5 -C} Ru atoms define the vertices of a square pyramid 9
Carbon atom tics slightly below the square base of RUs .
a variety of structures may be found. Selected examples of clusters with nuclear- d(Ru -Ru) = 2 .83-2.85 A . d(Ru-C) = 2 .04 A .
ity five are described in Table 2 .4. Some of the geometries occurring in pentanuc- Os5(CO),,(P,-C) Isostructural with Fe,-C(CO),s . 10
lean clusters are schematically illustrated in Fig . 2 .17 . Low symmetry arrays may d(Os -Os) = 2 .85-2.88 A; d(Os-C) = 2.06 A.
be formally derived from the trigonal bipyramide . Structure b in Fig . 2 .17 can be [Ob,(CO)I s(p s -C)I] Bridged-butterfly open structure in which the metal 10
considered as arising from breaking one equatorial metal-metal bond of the atoms define five' of the seven vertices of a pentagonal
trigonal bipyramide . The scission in the same polyhedron also of one bond but bipyramid (arachno geometry) (Fig. 2 .17d). Carbido
a tom approximately at the centre of the
an axial one gives rise to the edge-bridged tetrahedral geometry c. From poly hedron.
poly
structures b and c the structures with bow-tie, d, and bi-diminished pentagonal Os 5 (CO) 19 Metal-atom skeleton build by two triangles sharing 11
bipyramid, e, geometries can be derived by rupture of two and one bonds a vertex (Bowtie geometry Fig . 2 .17d). d(Os-0s)
respectively . These geometries are related, as it will be seen in the next section, involving common vertex are rather longer
(291
. 2)
.945than the ocher A85 cwo . (2)A.
by changes in the number of cluster electrons .
os 5{co), 6{P(oMe) 3 j 3 Structurally similar to Os 5(CO),, in which three CO 11
Solid angles and distortion degree in open structures depend on a number of groups have been replaced by phosphite ligands .
factors as, for instance, the number of electrons, the nature of disposable Os 3 (CO),AP 5 -n 2 -C 2 PPh 2 )(p-PPh r ) Three edge-fused Os 3 triangles with a "swallowlike" 12
orbitals, and the properties of the ligands . arrangement . PPh 2 group bridges the non-fused edge
of the central triangle, d(Os-0s) = 2 .742-2 .934 A.
Co s(CO) 9(p-CO) 2(p-PMe 2 )3 Trigonal bipyramidal arrangement of Co atoms with 13
one Co(ax)- Co(eq) bond ruptured (edge bridged
Table 2A. Selected examples of pentanuclear metal clusters tetrahedron . Fig . 2.17c) . d(Co-Co) in central Co 3 (CO)b
unit : 2 .41-2.47 A .
Compounds Remarks Ref. [Rh,(CO),o(p-CO)5]- Metal atoms form a trigonal bipyramid (C 2 ). (p- 14
CO-bridges are spanning the vertices of equatorial
V5(143-S)6(Cp15 VCp' units form a trigonal bipyramid fate-capped by 1 plane and two basal-apical edges . d(Rh-Rh) = 2.73 A
S'atoms . d(V-V) = 3 .062 (eq-ax) and 3 .2(16 A (eq-eq). (eq . plane) and 2 .923-3 .032 A .
[Cr .(p-SCMe 3 )(p 3 -S)(Cp) 2 ] 2 Cr Pentanuclear "bow-tie" frame (see Fig. 2 .17d) with 2 Ir 5(CO) e (p-CO) 2(p4 -Ph)(Cp') Square-pyramidal metal skeleton with the (p 4 -PPh) 15
a central Cr(H) atom . Angle between the triangle planes group capping the square base
90' . Sulfur atoms cap the Cr 3 triangle. Thiolace groups d(lr-11r) = 2 .747 2 .784 A .
are bridging peripheral Cr atoms which are each other
[Ni 5 (CO} y(P-CO).,(Et-CO) 3 }- Ni 3(CO} 3 {p-CO) 3 unit is capped by two Ni(CO) 3
double-bonded (2 .655 A). d(Cr-Cr) (between central groups. d(Ni •- Ni) 2.36 (eq) and 2.742.865 A (ax).
and peripheral atoms) = 2 .889-2 .933 A.
Pt 5 (CO)(yt 2-CO) 2 (p-S0 2 ) 3(PPH 3 ), Pt atoms arranged as the corners of an edge-bridged- 16
fMosCl,3] 2- Square pyramidal Mo, unit (Fig . 2 .23}. ;
tetrahedron (bridged-butterfly geometry, Fig . 2-17c) .
Fe5(CO) 15 (u 5 -C) Fe atoms define a square pyramid with the carbide just 4 d(Pt- Pt) = 2.751-2 .877,k .
below the center of the basal plane . Cu,(mes) 5 mes = mesytil . Pentameric cyclic structure consisting 17
Fes(COI,3(p3-S)2(P,_CS) Fe atoms define the vertices of a 5 square . The fifth is 5 in a ten-mcmbered ring where Cu atoms bridged by
terminal to the square lying above the Fe 4 plane and Phenyl groups are forming a five-pointed star-shaped
forming with an edge of the square an open Fe, unit skeleton. d(Cu-Cu) = 2 .473-2 .469 A .
capped on each side by pi-S. CS group is capping the
Fe 4 plane . d(1'e-Fe) = 2.46 (capped edge) to 2.78 A . Au 5(mes) 5 %A = mesityl. Ten-membered rings of alternate Au 18
and C atoms similar to Cu,(mes) 5 .
Ru 5 (CO) 1 s (p 4 -PR) R = C„H 5 , CH, CH,CH 3 , CH .C 6H, . Square 6 d(Au-Au) = 2.692-2 .710 A .
pyramidal arrangement of Ru atoms with phosphor
ligand capping the square face .
Ru 5 (CO} 5(MeCN 1 Ps -C) Four 0 u-at oms form butterfly arrangement with the References
7
wing-type Ru atoms bridged by a fifth one (Fig . 2.17d) . 1 Eremenko 11 . Katugin AS, Pasynskii, AA, Struchkov Yu T, Shklover VE (1988) J . Organomet .
Carbido atom is located above the central Ru-Ru bond Chem. 345 :79
and is coordinated to all five Ru atoms . 2 Pasynskii AA, Eremenko IL, Orazsakhatov B, Gasanov G Sh, Shktover VE, Struchkov Yu T
Rus(CO) 13(p 4-PPh)(p,-q 6-C 6H4) Square Ru 4 unit bridged on one side by a Ru(CO) 3 L 8 (1984). J . Organomet . Chem. 269 :147
fragment (L - n Z -double bond of benzyne which is 3 Jodden K, Schnering HGV, Schafer H (1975) Angew . Chem- Internat . Edn. 14 :570
7 z- 7 r -r -coordinated to the former triruthenium unit . 4 Braye EH, Dahl LF, Hubel W, Wampler DL (1962) J- Am . Chem. Soc. 84 :4633


78 2 Transition Metal Cluster Chemistry 2 .2 Structural Characteristics of Molecular Metal Clusters 79

0
Table 2.4 . (continued) CO CO C
co OCR CO
5 Broadhurst PV, Johnson BFG. Lewis J, Raithby PR (1981) J . Am. Chem . Soc. 103 : 3198 O
6 Natarajan K, Zsolnai L, Hutiner G (1981) J . Organomet . Chem . 209 :85 oc OC
j~\ _c0
7 Johnson BFG, Lewis J, Nicholas JN, Oxton IA, Raithby PR, Rosales MJ (1982) J . Chem. Soc., ```~~~
Chem. Cotnmun., 289 oc \ ` o
OC--
8 Knox SAR, Lloyd BR . Orpen AG, Vinas JM . Weber M (1987) J . Chem . Soc., Chem . Commun., OC N0 C
, _CO CO
1498 OC
9 Farrar DH, Jackson PF, Johnson BFG, Lewis J, Nicholls JN, McPartlin M (1981) J . Chem . Soc., OC--
oc
Chem . Commun., 415 ~ _ C0 co
c 0
to Jackson PF, Johnson BFG, Lewis J, Nicholls JN, McPartlin M, Nelson WJH (1980) J . Chem. 0
0
Soc., Chem . Commun ., 564
11 Farrar DH, Johnson BFG, Lewis J, Raithby PR, Rosales MJ 11982) J . Chem. Soc., Dalton a b
Trans ., 2051
12 Daran J-C, Cabrera E, Bruce MI, Williams ML (1987) J. Organomet . Chem . 319 :239 Fig. 2.1& Examples of pcntanuclear clusters with square-base pyramidal geometries . (a)
13 Keller E, Vahrenkamp H (1977) Angew . Chem. Intern. Edn . 16 :731 [Fe,C(CO), 4 ] Z ; ( b) [Fe 5N(CO), 4 l
14 Fumagalli A, Koetzle TF, Takusagawa F . Chini P, Martinengo S, Heaton BT (1980) J . Am .
Chem . Soc. 102 :1740
15 Braga D. Vargas MD 119881 J . Chem . Soc ., Chem. Commun ., 1443
16 Briant CE . Evans DG, Mingos DMP (1986) J . Chem. Soc ., Dalton Trans ., 1535 electron-rich species need more open structures than the electron-deficient ones .
17 Gambarotta S, Floriani C, Chiesi-Villa A, Guastini C (1983) J . Chem . Soc., Chem . Commun., One special characteristic of open structures is the possibility of adding an atom
1156 or group capping the open face of the polyhedron . Square-based pyramidal
18 Gambarotta S, Floriani C, Chiesi-Villa A, Guastini C (1983) J . Chem . Soc ., Chem . Commun .,
1304 structures are indeed very appropriate for the inclusion of heteroatoms . Carbon,
nitrogen, sulfur, and phospholidene groups RP are known to occupy the
capping position on the square face of the pyramid leading thus to structures
that can be considered as closed polyhedrons . Cluster structures illustrated in
Fig . 2.18 may be thus considered as distorted octahedra . Examples of carbides in

411
penta and hexanuclear metal clusters are described in Chapter 3 .

i
The same type of stabilization by capping the open face of the polyhedron is

i(
a
Z/ d
observed for species with a bidiminished pentagonal bipyramidal geometry
(structure e in Fig. 2 .17) that, as noted above, has one metal-metal bond less
than the square-based pyramid .
Some pentanuclear osmium cluster complexes show structures with edge-
bridged tetrahedral geometries (c in Fig . 2 .17) . These structures have the same

y 1 number of metal-metal bonds as the square-based pyramid but only triangular

faces, so the stabilization of interstitial atoms is not possible there .

2.2.6 Hexanuclear Metal Clusters

Fig. 2.17. Types of geometries in pentanuclear clusters . (a) Trigonal bipyramid ; (b) Square pyramid :
There are an important number of clusters with nuclearity six . Organometallic
(c) Edge-bridged tetrahedron ; (d) Bow-tie geometry; (e) Diminished pentagonal bipyramid or
bridged-butterfly geometry as well as high-valence hexanuclear cluster species are indeed well represented .

High-Valence Metal Clusters . Structural properties of selected hexanuclear

From the point of view of the stability of clusters, which appears to be
preferred in the case of deltahedral geometries, the trigonal bipyramid should be
the most favorable structure for pentanuclear clusters . Many of known clusters
with nuclearity five indeed have this class of structure .
As it will be seen in next Section, metal cluster structures are closely related
to the number of electrons and orbitals existing in the cluster core . In general,
high-valence cluster complexes are described in Table 2 .5 . A series of molyb-
denum and tantalum derivatives of type [(M 6 Y a )X 6] z- and [(M 6Y 8 )L 8 ] 41-
(M = Mo or W: X = halide or alkoxide: Y = halide or other monovalent anion ;
and L = neutral Lewis-base) are known . The structures of these species are like
that of the anion [(Mo 6 Cl a )C16] z - illustrated in Fig. 2.19 in which the molyb-
denum atoms are in the vertex of an octahedron . Metal-metal distances of about


80 2 Transition Metal Cluster Chemistry 2 .2 Structural Characteristics of Molecular Metal Clusters 81

Table 23. Structural properties of selected high-valence hexanuclear cluster compounds Niobium and tantalum also give rise to hexanuclear cluster species . Many
ions with formulas [(M 6 Y 12 )X61 4 and [{M C Y 12 )L6 )2 (M = Nb or Ta;
Internuclear distances (A) Ref.
Compound Y = halides; X = halide or other monovalent anion ; L = neutral Lewis base)
M M M X M-x are known . Figure 2.20 illustrates the type of structure found for this class of
Bridged (Terminal) clusters. Metal atoms build octahedra which often undergo certain distortions
along the tetragonal axis . The twelve halide ions bridge all the edges of the
(Me4 N)h [Nb6(p2-Ct)12C16] 3.02 2 .43 2.48 1 octahedron . Metal-metal distances in these Nb or Ta clusters are about 2 .9 A,
3.07 2 .56 .46 2
(PyH)(PyH)z2[Nb[Nbs6(p(J22-Br-C1))6l2C16]
3 i .e . a value near to that of the interatomic distances in the pure metal (ca . 2.86 A).
(Pz - Br)6CI 6] 3.03 2.52 ,2.57 22.62 2
Nb6(p2-Cl),zC16 ;2 2.92 2.41 2.58 3 Similar compounds of scandium and zirconium are also known .
K 4[Nb6(p2-C0 12CI 61 2.91 2.49 2.60 4 The versatility of halide ligands able to act as terminal, edge and face-
Ta6(JtrCl)1 2C16 ;2 2.92 2 .43 2.56 5 bridging ligands often cause, similar to that which occurs for the ReC1 3 , the
H2[Tab(ft2-Cl) 12 ]6H2O 2.96 2 .41 2.51 6 clusters to be aggregated into more complex tridimentional extended structures .
[Mo6(f03-Cl) 5 C12]C14 ;2 2.61 2 .47 2.50 7
C82 [M0 6 (p3-Cl) s Br
6J 2.62 2.48 2.58 8
Cs21W6(P3-Cl)sBr61 2.62 2 .49 2.57 8
[W6(u3- Br)s Br 41Br4 2.64 2 .58 2.58 9 L

References Y = 1 Y.
.L
I Koknat FW and McCarlcy RE (1972) Inorg. Chem . 11 :812 /
2 Spreckelmeyer B, Schnering HG (1971) Z. Anorg. Chem . 386 :27 Y- 4 y
3 Simon VA, Schnering HG . Wohrle H, Schafer H (1965) Z. Anorg . AIIg. Chcm . 339 :155
4 Simon VA, Schnering HG (1968) Z . Anorg . AIIg . Chem. 361 :235
5 Bauer D, Schnering HG (1968) Z. Anorg. Chem . 361 :259
L
Y
4~ ] L

6 Thaxton CB, Jacobson RA (1971) Inorg . Chem . 10 :1460

7 Schafer H, Schnering HG, Tillack J, Kuhnen T, Wohrle H, Baumann H (1967) Z . Anorg . Chem .
353 :281 L Y om' y Y
8 Healy PC ,,,,
Kepert DL Tay ]or D White AH (1973) 1 "hem .Soc ., Dalton 646 Y
9 Siepmann R, Schnering HG (1968) Z . Anorg . Chem. 357 :289 2+
L Fig. 2.20. Schematic structure of cations [(M 6Y 12)L6 ]

C]

I I /, F
CI
CI
A
CI
F `F F /
CI
It
~kv
CI
r
CI`i Ct c\-'
~I .-F F ids F-
C1 ~lr f`
CI
t l
c1CI/ CI ` kj, 7 C] F v F
I
Fig. 2.19. Schematic structure of the anion -CI i
CI UMo6CI8 )C16 ] 2- Cl ; ~rt F F
F
Cl
2.65 A are shorter than those observed in the pure metals (2.725 A) . Eight F
~C` c~ 1
I CI Cl
chloride ions are coordinating the faces of the octahedron and six are linked
o b
terminally to the metal atoms. In these compounds, analogous to rhenium
halides, the distances metal-terminal halides are somewhat shorter than those Fig. 2.21. Extended structures arising from the condensations of (a) Niobium chloride Nb 6C1 14 and
associated to bridging halides . (b) Niobium flouride Nb 6 F, S


82 2 Transition Metal Cluster Chemistry 2 .2 Structural Characteristics of Molecular Metal Clusters 83

The replacement of neutral ligands by halides in [Mo6 Cl 8 L 8 ] 4 ' or
[Nb 6 Cl12L8] 2+ results indeed in the generation of extended structures as
illustrated in Fig . 2 .21 for two niobium halide derivatives.
Sulfur, selenium, tellurium, and antimony may also act as it-donor ligands to
form metal clusters of some early transition elements. Although the compounds
are often polymeric solids, structural determinations have shown that they are
built up by condensed cluster units . Many of these compounds e .g . the Chevrel-
Sergent compounds [M 6 S 8 ] M' (M' = Pb 2 +, Cu", and other divalent cations
[Chevrel R, Gougeon P, Potel M, Sergent M (1985) Solid State Chem . 57 :25])
(Fig . 2.22) show interesting magnetic and electrical properties .
Most of the known high-valence metal cluster species belong to the tri and
hexanuclear clusters discussed above . However, there arc also some examples of
oilCWNW-We 0 .1-6
• I
0 s!r~:
this type of cluster with nuclearities of four and five . As shown schematically in
Fig . 2 .23, the pentanuclear cluster anion [MSCl13] 2- can be considered as being
the result of a loss of one Mo-Cl unit from [Mo 6 C1 14 ] 2- . The structures
observed for the tetranuclear compounds may be also rationalized as a fragment
of the same type of octahedral compounds. The relationship between the
structure of the hexanuclear species [M0 6 X 8] 2- and those observed for Mo,
compounds is analyzed in Fig . 2 .24 .
Hexanuclear Organometalllc Clusters . Although the octahedral arrangement of
metal atoms is the most representative one for hexanuclear cluster compounds,
a number of other geometries have also been observed . The structural character-
istics of a selected group of hexanuclear compounds are briefly described in
Table 2 .6. The different types of structures found for these clusters are illustrated
schematically in Fig. 2 .25 .
Among hexanuclear cluster with an octahedral array of metal atoms and
twelve metal-metal bonds, a number of inclusion compounds with interstitial
atoms should also be counted, e .g. carbon and hydrogen atoms located inside
the octahedron . Further examples of these types of compounds are described in
Chapter 3 .
An interesting feature being observed in Table 2 .6 and in Fig. 2 .25 is that
from the types of geometries adopted by hexanuclear clusters all, but the

40 0• ••4̀•4•+
octahedron and the trigonal prism, derive from other more simple arrangements
• by sharing additional atoms to edges or faces of polyhedra of lower nuclearity .
~. Thus, the bicapped tetrahedron also with twelve metal-metal bonds is an
!. alternative to the octahedron .
0 •!•! • i The capped square-based pyramid is an open structure with eleven metal-
o Mo • •0 metal bonds . The open, square face is frequently shared by a p,-face-bridging
O S rw, • ~~ 0 ft
e
0 M' 4:~' ~~ Fig. 2 .22, Schematic structure of
a Chevrel-Sargent phase
Y
Y
X
Ct Y
Cl
x-

S` Cl Cl

P
Cl Y
Ct \ Cl "Cl
CI 7\ I ." Cl
Y x
r ,. r
I
i
/'
,`
CI-.- , CI . Cl
Cl
A Mo 6 Y B
Cl
1-1 cc
CI Ct
cl~~ I 'V -
'CI Y /Y
Cl Ct
Y f -x
~~ \ x
ct ; x-
Yx Y Fig. 2.24. Relationship between
Fig . 2.23. Schematic structures of the anions [M 5C1 13 ] 2- M = MD, W and their relationship with M04 -compounds and the hexa-
the hexanuclear species Y molybdenum species [Mo 6 X a ] 2

2 Transition Metal Cluster Chemistry
84
Table 2.6. Selected examples of hexanuclear metal clusters
Cluster
Tib(ps-O)e(CP)6
[M6(N-X)12X6]"-
[M6(p3-l)8Y+
M 6 (p 3-X) e y4
Mo6(p3-Cl)8(Cl)2(Et)2(PBu3)2
[Fe ti (CO), 3 (p-CO)(p6-C)] 2-
Ru 6 (CO) 16 (p-CO)(p b -C)
[Ru 6 (CO) 2O (CN) 2 ]
Ru 6 (CO), 3 (p-CO)(-C6 H3Me)1p 6 -C)
Os 6 (CO) 18
Os 6 (CO) 18 _,(PPh 3 )„
[Os6(CO)1s(p6-P)] -
Os6(CO) i 6(p3-NCMe)(p4-CMe)
Os6(COl 111 (p 3-S)(u 4 -S)
[Co6 (CO) 1;( p3-CO) e ] 4-
Co 6 (CO), 6 (p-rl 3-C ZS 2 )(p3-S)
Remarks Ref.
Ti atoms define the vertices of a regular
octahedron. d(Ti-Ti) = 2 .891 [shorter than
in metal (2 .951 A)] .
M = Nb,Ta ; X = Cl, Br; n = 2, 4 . d(M-M) 2-9
= 2 .91-3.07 A . M 6 unit has regular
octahedral geometry .
M = Nb,Ta; n ~ 2, 3 .
M = Mo, W ; X, Y = Cl, Br . Metal atoms
define the vertices of a little distorted
octahedron. d(M-M) = 2.61-2 .64 A.
Ethyl groups, two chlorine atoms, and
two tributylphosphine groups are bounded
to the M0 6CI s core in mutually trans
positions . Cluster core dimensions are
almost the same as that of the chlorine
complex.
Carbide atom lies in the centre of a Fe.
octahedron .
Octahedral arrangement of Ru atoms with
carbon atom in the centre.
d(Ru-Ru) = 2 .05 A .
Two parallel Ru triangles linked by two
axial CN-bridges . d(Ru-Ru) = 2 .870-2.88 A .
Carbide atom nearly in the centre of a Ru b
octahedron . d(Ru-Ru) = 2-815-2 .955 A .
Bica P r d tetrahedron. d(Os-Os) = 2,754 A
tral tetrahedron and 2 .731 A° in
in central
bonds with the other two Os atoms .
n = 1 . 2 . Substitution of CO groups by
phosphine ligands on capped
in Os 6 (CO), e .
Trigonal prismatic Os 6 unit containing an
interstitial P atom that coordinates all six
metal atoms. d(Os- Os) = 2 .930 (basal
triangle) and 3 .140 A (inter-basal edges).
Os atoms define the vertices of a mono-
capped square pyramid. CMe groups arc
capping, one the square plane . and the
other, an adjacent triangular face .
A square-pyramidal cluster of five Os
ake with a S metal s
batoms
m a ns
o f . The sixth metal atom
atombridges the an edge
square
s
th square base forming a
capped by the second S atom. Common
edge is unusually short (2 .686 A).
Distorted octahedron, d(Co-Co) = 2,49A
(av .)
Two different Co 3 units linked by the
CCS 2 ligand .
2 .2 Structural Characteristics of Molecular Metal Clusters 85
Table 2 .6. (continued)
Cluster Remarks Ref.
I [Co6 (COI y (p-COJ4()u 6 -N)] - Octahedral array of Co atoms with 26
mtersttctal N atom.
Cos(CO),2(p3- S)2(po-C) Trigonal prism with the two ends capped 27
by S atoms . d(CO-CO) = 2 .437 and
2.669 A in triangles and rectangular faces
respectively .
10 Rh 6 (CO) 12 (p 3-CO)4 Rh6 (CO), 2 octahedron . d(Rh-Rh) = 2.776 A . 28
t 1-13 [Rh 6 (CO)„(p 3 -CO)4 1] - Derived from Rh 6 (CO)„ by replacement 29
of CO by iodine . d(Rh-Rh) = 2 .746 A .
[Rh 6 (CO) 7 (p-CO) ;(pn -Cl] 2- Distorted octahedron of Rh atoms with 30
14 the carbide in the centre.
d(Rh-Rh) = 2 .733-3 .188 A .
[Rh6 (CO) 8 (p 3 -CO)4 {P(OPh) 3 },] Rh atoms define the vertices of a slightly 31
distorted octahedral cluster.
d(Rh-Rh) - 2 .789 A . P(OPh)3 ligands are
bound to four equatorial coplanar Rh atoms .
15 [Rh6 (CO) 11 (p-CO) 4(rl 3 -C 3 H s )] - Octahedral arrangement of Rh atoms, 32
Allyl ligands are bonded to one of the
16 Rh atoms . d(Rh-Rh) = 2,703-2 .822 A .
[Rh6 (CO) 6 (p-CO), (dppm)( ;:6-C}]2- Rh atoms define a distorted octahedron 33
containing interstitial carbide .
17 d(Rh-Rh) = 2.76 and 3.05 A for the
CO-bridged and unbridged edges respectively .
18 [lr6(CO) 1 2(p-CO)3J 7 Octahedral Irb cluster with three symmetri- 34
cal edge-bridging carbonyl $roups .
19 d(ir--ir) = 2 .736 and 2,785 A for bridged
and unbrtdged edges respectively,
Ni 6 (Cp) 6 Ni atoms are located at the corners of an 35
20 octahedron with a Cp-ligand coordinated
Os atoms at each metal atom . dt Ni-Ni) = 2 .44! A .
Pt 6 (p-Cl) 12 Ptb octahedron with a structure similar to 36
21 Nb and Ta halides [M6X 12 ] 2+ (vide supra).
d(Pt-Pt) - 3 .32-3 .40 A,
Cu6 (p .1-2-McNCb H4 )4 (p-Br) 2 Distorted octahedron . 37
d(Cu-Cu) = 2 .64-2 .70 A .
22 [Aub{P(C6H7)3}6] 2+ Distorted octahedron . 38
d(Au-Au) = 2.932-2 .990 and 3.043-3 .091 A.
23 References
I Huftman JC, Stone JG, Krusell WC, Caulton KG ( 1977) J . Am . Chem . Soc . 99 : 5830
2 Koknat FW, McCarlcy RE (1972) Inorg . Chem. 11 :812
3 Field RA, Kepert DL . Robinson BW . White AH (1973) J. Chem . Soc ., Dalton Trans., 1858
4 Spreckelmcyer B, Schncring HG (19711 Z. Anorg. Chem . 386 :27
5 Simon VA . Schnering HG, Wohrle H, Schafer H (1965) Z . Anorg. AlIg . Chem . 339 :155
24 6 Simon VA, Schnering HG (1968) Z . Anorg. AlIg, Chem . 361 :235
7 Bauer D, Schnering HG (1968) Z . Anorg. Chem . 361 :259
25 ti Thaxton CB, Jacobson RA (1971) Inorg . Chem . 10 : 1460
9 Burbank RD (1966) Inorg . Chem . 5 : 1491


86 2 Transition Metal Cluster Chemistry 2.2 Structural Characteristics of Molecular Metal Clusters 87

Table 2.6. (continued) Table 27. Examples of clusters with seven and more metal atoms

10 Bateman LR . Blount JF, Dahl LF (19661 J . Am . Chem . Soc . 88 : 1082 Compound Type of Number of Ref.
I1 Healy PC . Kepert DL, Taylor D, White AH (1973) J . Chem . Soc ., Dalton, 646 structure valence
12 Schiifer H . Schnering HG, Tillack J, Kuhnen T, Wohrle H, Baumann H (1967) Z . Anorg. Chem . in fig . 2 .26 electrons
353 :281
13 Guggenberger LJ, Sleight AW (1969) Inorg . Chem. 8 :2041 Seven metal atoms
14 Saito T . Nishida M, Yamagate T, Yamagata Y . Yamaguchi Y (1986) Inorg. Chem . 25 :1111 [Re,C(CO) 22 ] - a 98 1
15 Churchill MR, Wormald J . Knight J, Mays MJ (1971) J . Am . Chem . Soc. 93 :3073 Os7lCO) 2 , a 98 2
16 Sirigu A, Bianchi M, Benedetti E (1969) J . Chem . Soc ., Chem . Commun ., 596 [Rh,(CO)„]3- a 98 3
17 Lavigne G . Lugan N, Bonnet J-J (1987) J . Chem . Soc., Chem. Common . . 957 Ir,(CO), 2 (C g H, 2 )(CgH„)(C a H 1 0) a 98 4
18 Farrugia LJ (1988) Acta Crystallogr . C44 :997
19 Mason R, Thomas KM, Mingos DMP (1973) J . Am. Chem . Soc. 95 :3802 Eight metal atoms
Pd a (CO) g (PMe 3 ), b [to 5
20 Couture C, Farrar DH, Gomez-Sal MP, Johnson BFG, Kamarudin RA, Lewis J, Raithby PR
[Re s C(CO) 24 ] 2- c I to 6
(1986) Acta Crystallogr . Sect. C42 :163 [Os5 (CO) t2 ] 2- c I to 7
21 Colbran SB . Hay CM, Johnson BFG, Lahoz FJ, Lewis J, Raithby PR (1986) J . Chem . Soc.,
Chem . Commun ., 1766 Nine metal atoms
]2
22 Eady CR, Femandez JM . Johnson BFG, Lewis J, Raithby PR . Sheldrick GM (1978) [Co" Si(CO)21 d 129 8
J . Chem . Soc, Chem . Commun ., 421 [Rh9 (CO) 19 ] 3- e 122 9
23 Adams RD, Horvath IT, Yang LW (1983) J . Am . Chem. Soc . 105 :1533 [Rh,, P(CO)21 ] 2 - d 130 10
24 Albano V, Bellon PL, Chini P, Scatturin V (1969) J . Organomet . Chem. 16 :461 [Ge9 ] 2 - f 128 11
25 Stanghellini PL, Gervasio G, Rossetti R, Bor G (1980) J . Organomel . Chem. 187 :C37 [Ge9 ] 4- d 130 11
26 Ciani G, Mertinengo S (1986) J. Organomet . Chem. 306 :C49 [Bi 9 ]s' f 130 12
27 Bor G, Gervasio G . Rossetti R, Stanghellini PL 11978) J . Chem . Soc., Chem . Commun . . 841 Ten metal atoms
28 Paquette MS . Dahl LF, 11980) J. Am . Chem Soc. 102 :6621 [Os, O C(CO) 24 1 2 g 134 13
29 Albano VG, Bellon PL, Sansoni M (19711 ) Chem . Soc . (A) 678 OS io C(CO) 23 (POMe 3 )I 2 g 134 14
30 Albano VG, Braga D, Martinengo S (1981) J . Chem . Soc., Dalton Trans ., 717 [Os 10 C(CO) 22 (NO)1] 2- g 136 14
31 Ciani G, Manassero M, Albano VG (1981) .I, Chem . Soc ., Dalton Trans., 515 [Rh 10 P(CO) 22 ] h 142 15
32 Ciani G, Sironi A, Chini P, Ceriotti A, Martinengo S (1980) J . Organomet. Chem . 192 :C39 [Rh, O S(CO)22 ]2- h 142 16
33 Bordini S, Heaton BT, Seregni C, Strona L, Goodfellow RJ, Hursthouse MB, Thornton-
Pd 10 (CO) 14 (PBu 3 )4 t 136 17
Pett M . Martinengo S (1988) J . Chem . Soc. . Dalton Trans ., 2103
34 Demartin F, Manassero M . Sansoni M, Garlaschelli L, Martinengo S, Canziani F (19801 Eleven metal atoms
J. Chem . Soc., Chem. Commun ., 903 [Os,,, A UCICO1 24 (PPh 3 ) ] J 146 18
35 Paquette MS, Dahl LF (1980) J . Am. Chem Soc. 102 :6621 [Rh 11 (CO) 23 ] 3 k 148 19
36 Brodersen K, Thiele G, Schnering HG (1965) Z. Anorg. Chem . 337 :120 [Rh 9 P1 2 (CO) 22 ] 3- k 148 20
37 Guss JM, Mason R, Thomas KM, van Kolen G . Noltes JG (1972)J, Organomet . Chem . 40 :C79 Au 11 (PPh 3 ) 7 (SCN) 3 1 138 21
38 Bellon P, Manassero M, Sansoni M (1973) J . Chem . Soc., Dalton Trans,, 2423 Au, I (PPh 3 ),1 3 1 138 22
Twelve metal atoms

4
[Rh,,C 2 (CO)24 ] 2- m 166 23

60 &f
[Rh, 2 C 2 (CO)S3 ] 3- m 167 24
[Rh, 2C2(CO)23 ] 4 m 168 25
[NiQ As 3 (CO) 15 Ph 3 ] 2 n 170 26
~1 , [Ni, o As 2 (CO), g Met ) 2 n 170 26
Thirteen metal atoms
IF [HR h 13(C0124 3(C )124j4- 0 170 27
[H 2 Rh131CO)24] 3 o 170 28
[Au1 j(PMcPh2),o] 3 ' p 162 29
[Au, 3) Ph 1 PCH 2 PPh 2 )v ] 4 h p 162 30
Fourteen metal atoms
[Rh,4(CO)2,] 2 _ q 180 31
[Rh,4(CO)25] 4 q 180 32
Fifteen metal atoms
[Pt, 5ICO)3o] 2- r 212 33
f 9 h I J Sixteen metal atoms
Fig. 2.25. Types of structures frequently adopted by hexanuclcar metal clusters . (a) Octahedron [Ni 15(CO)23 (C2 )2 ]4 s 216 34
(b) hicapped tetrahedron ; (c) capped square pyramid ; (d) edge-sharing bitetrahedron ; (e) trigonal-
prism ; (f) six-atom-raft triangles; (g) six-atom-raft rhomb; (h), (i), and (j) edge-bridged hi-diminished Seventeen metal atoms
bipyramidal or edge-bridged butterfly geometries [Rh, 74C06013- t 216 35


89
2 .2 Structural Characteristics of Molecular Metal Clusters
88 2 Transition Metal Cluster Chemistry

Table 2.7. (continued) 2.2.7 Clusters with Seven or More Metal Atoms
References .7, a select group of organometallic clusters with different nuclearities
In Table 2
I Beringhelli T, D'Alfonso G, De Angelis M, Ciani G, Sironi A (1987) J . Organomet . Chem . . Geometries adopted by some of the structures of large clusters in
are described
322 : C2 this table are shown schematically in Fig . 2.26.
2 Eady CR, Johnson BFG, Lewis J . Mason R, Hitchcock PB, Thomas KM (1977) J . Chem. Sec., The tendency towards the formation of structures formally produced by the
Chem. Commun ., 385
3 Albano VG, Bellon PL, Ciani G (1969) J . Chem . Soc., Chem . Commun ., 1024 condensation of structures of lower nuclearity by sharing edges and faces
4 Pierpont CG (1979) Inorg . Chem. 18 :2972 observed for hexanuclear clusters is reinforced in larger clusters .
5 Bachmann M, Hawkins 1, Hursthouse MB, Short RL (1987) Polyhedron 6 :1987
6 Ciani G, D'Alfonso G, Freni M, Romiti P, Sironi A (1982) J . Chem . Soc., Chem . Commute„ 705
7 Jackson PF, Johnson BFG, Lewis J, Raithby PR (1980) J . Chem . Soc., Chem . Commun., 60
8 Mackay VM, Nicholson BK, Robinson WT, Sims AW (1984) J . Chem . Sec., Chem. Commun.,
1276
9 Martinego S, Fumagalli A, Bonfichi R . Ciani G, Sironi A (1982) J. Chem . Sec., Chem . Commun,
825
10 Vidal JL, Walker WE, Pruett RL, Schoening RC (1979) Inorg . Chem. 18 :129
11 Belin CHE, Corbett JD, Cisar A (1977) J . Am. Chem . Soc. 99 :7163
12 Friedman RM, Corbett JD (1973) Inorg. Chem . 12 :1134
13 Jackson PF, Johnson BFG, Lewis J, Nelson WJH, McPartlin M (1982) J . Chem . Sac ., Dalton
Trans ., 2099
KW
14 Goudsmit RJ, Johnson BFG, Lewis J, Nelson WJH, Vargas MD, Braga D, McPartlin M, Sironi • d e
A (1985) J. Chem . Sec ., Dalton Trans ., 1795 a b c
15 Vidal JL, Walker WE, Schoening RC (1981) Inorg . Chem. 20 :238
16 Ciani G, Garlaschelli L, Sironi A, Martinengo S (1981) J . Chem. Soc ., Chem . Commun., 536
17 Mednikov EG, Eremenko NK, Slovokhotov YL, Struchkov YT, Gubin SP (1983) J . Organomet .
122222-
Chem . 258 :247
18 Brags D, Henrick K . Johnson BFG, Lewis J, McPartlin M, Nelson WJH, Vargas MD (1986)
J. Chem . Sec ., Chem . Commun ., 975
N* 01 Ile15,
19 Fumagalli A, Martinengo S, Ciani G, Sironi A (1983) J . Chem. Sec., Chem. Commun ., 453
20 Fumagalli A, Martinengo S, Ciani G (1984) J . Organomet . Chem . 273 : C46
21 McPartlin M, Mason R, Malatesta L (1969) J. Chem . Soc ., Chem . Commun. 334 h 1 1
22 Smits JMM, Beurskens PT, Van der Velden JWA, Bour JJ (1983) J. Cryst. Spectrosc. 13 :373 9
f
23 Albano VG, Braga D, Chini P, Strumolo D, Martinengo S (1983) J . Chem. Sec., Dalton Trans .,
249
24 Albano VG, Braga D, Martinengo S, Seregni C, Strumolo D (1983) J . Organomet . Chem . . ~ .`rte';.
r
252 : C93
25 Albano VG, Braga D, Strumolo D, Seregni C, Martinengo S (1985) J . Chem . Sec .. Dalton Trans .,
,.~'•=.;
14 •~ .,.;;.~ ~ ~,
1309 '~
26 Rieck DF, Montag RA, McKcchnie TS, Dahl LF (1986) J . Am. Chem . Soc. 108 :1330
27 Ciani G, Sironi A, Matinengo S (1981) J . Chem. Sec., Dalton Trans ., 519
28 Albano VG, Ciani G, Martinengo S, Sironi A (1979) J . Chem . Soc., Dalton Trans. . 978
•
m n 0
29 Briant CE, Theobald BRC, White JW, Bell LK, Mingos DMP (1981) J. Chem. Soc ., Chem . k L
Commun, 201

AMk
30 Van der Velden JWA, Vollenbroek FA, Bour JJ, Beurskens PT, Smits JMM, Bosman WP, (1981)
R ec. 1 . R . Neth . Chem . Sac. 100 :148
31 Martinengo S, Ciani G, Sironi A (1980) J . Chem . Sec., Chem . Commun ., 1140
32 Ciani G, Sironi A, Martinengo S (1982) J . Chem . Soc., Dalton Trans., 1099 •~~. 000
`~/*
`;
33 Calabrese JC, Dahl LF . Chini P, Longoni G, Martinengo S (1974) J . Am . Chem . Soc. 96 :2614
34 Ceriotti A, Longoni G, Manassero M, Masciocchi N, Piro G, Resconi L, Sansoni M (1984) Role
J . Chem. Soc ., Chem. Commun. 1402
35 Ciani G, Magni A, Sironi A, Matincngo S (1981) J . Chem . Soc. . Chem . Commun ., 1280 q S t
P
. Examples of types of geometric arrangements of metal atoms found in large clusters
ligand as occurs for instance in Os 6 (CO) 17S . There are however compounds in Fig. 2 .26
which the square face remains open as found in H20s 6(CO) 1a .
Trigonal prismatic structures are not found very often in simple hexanuclear
clusters . Most compounds with this metal atom arrangement are carbides and
nitrides in which the heteroatom occupies the center of the prism .

90 2 Transition Metal Cluster Chemistry
2.3 Bonding in Metal Clusters
As discussed in the last section, the metal network in clusters may be considered,
especially for high nuclearity clusters, as a finite portion of a compact metal
structure stabilized by external ligands . The feature that the number of atoms is
relatively small does not make the description of the system simpler . On the
contrary, for pure metals as well as for traditional mononuclear compounds,
there are theories which allow us to produce descriptions of their properties
which, however, do not fit for clusters . In the very short history of this new class
of compounds many efforts have been made to obtain some generalizations that
permit us to rationalize experimental features as being structures and reactivity,
as well as to perform quantitative theoretical calculations . The most important
approaches to bonding in metal cluster are summarized in Table 2 .8 .
Since cluster compounds in general are rather complex species the applica-
tion of quantitative methods for describing bonding is not only difficult but also
impractical . Qualitative approaches and empiric rules often play an important
role in this case . Simple methods permitting the systematization and projection
of known features are very valuable for practical chemists .
Table 2.8. Relevant concepts and approaches to chemical bonding in main group and transition
metal clusters
Approach
Remarks Ref.
Description
The Effective A(ornic Number WAN(
The total number of cluster valence electrons 1
or Inert-Gas Rule
(i .e . metal valence electrons plus those apported
by the ligands) is such that each main group
atom as well as each transition metal atom in
the cluster has 8 and 18 electrons respectively .
Clusters which follow this rule are known as
"electron precise species-
Polyhedral Skeletal Electron Pair Bonding pattern in metal clusters is analogous 2-9
Theory to that in the boranes (electron defficient
species) where each atom contributes with
3 orbitals and 2 electrons to the skeletal
bonding.
Dever Principle The addition of secuensive pairs of electrons to 4, 10,
a closo-cluster opens its structure originating 11
nido and arachno structures, i .e . producing the
remotion of cluster vertices (decapping) .
Isobal Analogy
There are definite similarities between the 12-16
number energies, shapes, and nodal
characteristics of both main group and
transition metal carbonyl fragments . This
analogy has proved to be useful in accounting
structural similarities between main group and
transition metal clusters .
Capping Principle
CapF in8 a face by a ML s fragments or bridging 8,9
an edge by a C a ,.-ML, fragment on a given 17,18
polyhedron leads to no change in the number of
skeletal bonding MOs.
2 .3 Bonding in Metal Clusters 91
Table 2.8. (continued)
Approach Remarks Ref.
Description
Polyhedral Fusion Condensed clusters may be regarded as the 19,20
product of two or more polyhedra sharing
a vertex, an edge, or a face .
Polyhedral Inclusion High nuclearity cluster may be formally divided 21,22
into an incapsulated, internal polyhedron and
other surface, external polyhedron .
Free electron cluster bonding models Skeletal bonding is described in terms of a free 23
electron bonding model similar to those used for
bulk metals.
Tensor Surface Harmonic theory Cluster atoms are constrained to lie on the 24-28
surface of a single sphere cluster, molecular
orbitals are thus derived from a spherical
potential model .
Graph-Theory derived Approach Ideas derived from topology and graph-theory 29-33
are used to model the skeleton chemical
bonding in clusters .
References
1 Sidgwick NV, Powell HE (1940) Proc . Roy . Soc. A176 :253
2 Teo BK (1984) Inorg. Chem . 23 : 1251
3 Teo BK, Longoni G, Chung FRK (1984) Inorg . Chem . 23 :1258
4 Wade K (1971) J . Chem . So c., Chem . Comm ., 792
5 Wade K (1976) Adv . Inorg. Chem. Radiochem . 18 :1
6 Wade K (1972) Inorg. Nucl . Chem. Lett . 8 : 559, 563, 823
7 Wade K (1972) Nature Phys. Sci . 240 :71
8 Mingos DMP (19721 Nature Phys . Sci. 236 :99
9 Mason R, Thomas KM, Mingos DMP (1973) J . Amer . Chem. Soc . 95 :3802
10 Rudolph RW, Pretzer WR (1972) Inorg Chem . 21 :1974
A
It Rudolph RW {1976) Acc Chem. Res . 9 :44(:
12 Eli an M, Hoffmann R (1975) Inorg . Chem . 14 :1058
13 Elian M . Chen MML, Mingos DMP, Hoffmann R (1976) Inorg. Chem . 15 :1148
14 Hertler WR, Klanberg F, Muetterties EL (1967) Inorg. Chem. 6 : 1696
15 Hoffmann R (1981) Science 211 :995
16 Hoffmann R (19821 Angew . Chem . Int . Edn . 21 :711
17 Mingos DMP, Forsyth Ml (1977) 1 . Chem . Soc., Dalton Trans. . 610
18 Evans DG, Mingos DMP (19831 Organontetallics 2 :435
19 Mingos DMP (1983) J . Chem. Soc ., Chem . Comm ., 706
20 Mingos DMP (1984) Ace . Chem. Res . 17 : 311
21 Mingos DMP 11985) J . Chem. Soc.. Chem . Comm ., 1352
22 Mingos DMP (1986) Chem . Soc Rev . I5 : 31
23 DeKock RL, Gray HB (1980) Chemical Structure and Bonding . Benjamin/Cummings, Menlo
Park (California), p. 419
24 Stone CJ (1980) Mol . Phys . 41 : 1339
25 Stone AJ (1981) Inorg . Chem . 20 : 563
26 Stone Al . on Nil (t982) Inorg. Chem . 21 :2297
27 Stone AJ (1 984) Polyhedron 3 :2051
28 Fowler PW, Porterfield WW (1985) Inorg . Chem. 24 :3511
29 King RB . Rouvray DH (1977) J . Amer . Chem. Soc. 99 :7834
30 King RB (1981) Inorg . Chim . Acta 49 : 237
31 King RB (1982) Polyhedron 1 : 132
32 King RB (1986) Inorg . Chim . Acta 116 :99, 109, 119, 125
33 King RB (1990) Isr_ J . Chem . 30 :315


92 2 Transition Metal Cluster Chemistry 2.3 Bonding in Metal Clusters 93

23.1 The Inert-Gas Shell Configuration Approach electrons donated by the ligands . Thus the number of electrons available for
metal-metal bonds is given by following relationship .
Mononuclear Metal Complexes . A large proportion of mononuclear transition
Number of electrons _ 2 x (Number of Total number
metal complexes can be considered to posses 18 electrons around the metal
in Metal-metal bonds metal orbitals) + of electrons
atoms, i .e . an inert-gas shell configuration . The central metal atom utilizes its
nine metal valence orbital-one s, three p and five d orbitals-to accommodate As it will be seen below, the counting of the electrons in the cluster can
both metal valence electrons and ligand electron pairs . These features constitute provide information not only about the number of the metal-metal bonds and
the well-known Effective Atomic Number (E .A .N .) or 18-electron rule . The large the presence of multiple bonds but also about the geometry of the metal
majority of low oxidation states, diamagnetic complexes specially binary car- polyhedron .
bonyls and other compounds with it-acceptor ligands, obey this rule . Indeed, the A number of selected examples of the application of the 18-electron rule to
rule has been exceptionally successful as a means of both predicting and a number of clusters with different nuclearities are described in Table 2 .9 .
rationalizing the structures of low-oxidation state, transition metal complexes . Predicted structural features are also compared there with the experimental
Exceptions do occur, particularly with dR metal ions, where many examples of evidences.
16-electrons (square-planar) complexes are known . In these complexes the It is easy to see in Table 2 .9 that successfully application of the rule to cluster
p 2 orbital has a relative high energy and it is found to be non-bonding and carbonyl systems is in general restricted to the smaller cluster containing five or
empty. Exceptions to the 18-electron rule are also found for the group 11 . Au(I) fewer metal atoms . However, also among the low nuclearity clusters there are
forms primarily two-coordinate, 14 electron complexes. Such deviations may be
considered to be due to the relatively large s (or d) -p promotion energies found
Table 2.9. Application of the effective atomic numbers (EAN) or 18-electron rule to metal clusters
for the free atoms . As discussed in Chapter 1, as the atomic number increases
across a transition metal series, the energy of the s and d orbitals drops more Compound Number or valence electrons Number of Number of Geometry
rapidly than that of the p orbitals thus increasing the s (or d) -p promotion electrons metal-metal
Metal Ligands Total after bonds
energies . atoms available inert-gas rule
The 18 electron-rule normally does not apply to transition metal complexes
[Re 3 C1 12 ] 3- ' 12 30 42 54 6 Triangle
with 7r-donor ligands and metal atoms in normal oxidation states . In this case
Fe 3 (CO) 1t 24 24 48 54 3 Triangle
the metal orbitals with 7r-symmetry lie at relatively high energy and they stay Os3(CO), 0 H 2 b 24 22 46 54 4 Triangle
empty or are only partially filled. In this way the formation of paramagnetic [Mn 3 (CO) 14 ] - 22 28 50 54 2 Chain
species can be possible . Ru 3 (CO) 6 (Cp) 2 ` 24 26 50 54 2 Chain
[Re4 (CO)16 ] 2- 28 34 62 72 5 Butterfly
Metal Clusters . The 18-electron rule as an approach to the bonding in metal geometry
Re 4 (CO) 12 H, 28 28 56 72 8 Tetrahedron
cluster supposes the skeletal atoms are held together by a network of localized [Fe4 (CO) 13 ] 2- 34 26 60 72 6 Tetrahedron
bonds and that each individual cluster atom utilizes its nine atomic orbitals to Co 4 Cp 4 H4b•` 36 24 60 72 6 Tetrahedron
form metal-metal bonds as well as to accommodate both metal valence electrons Pt,(CH 3 CO 2 ), 32 32 64 72 4 Square planar
and ligand electron pairs . Consequently, in the application of the 18-electron Fe 5 C(CO) 1 , 40 34 74 90 8 Square pyramid
Os 5 (CO), 6 40 32 72 90 9 Trigonal
rule to clusters, the following three assumptions should be taken into account :
bipyramid
1 . Metal-metal bonds are localized on the polyhedron edges. Os S S(CO) 15 40 34 74 90 8 Square pyramid
2. All metal-metal bonds are two-center/two-electron bonds . [Ni s (CO), 2 ] 2- 52 24 76 90 7 Trigonal pyramid
Ru 6 C(CO)„ 48 38 86 108 11 Octahedron
3 . Ligands are in general one electron pair donors irrespective of their charges . Os 6 (CO),A 48 36 84 108 12 Bicapped
Cyclopentadiene (7r-Cp) and arenes are 5 and 6 electron donors respectively . tetrahedron
[Co 5 (CO), 5 ] 2- 56 30 86 108 11 Octahedron
The number of metal-metal bonds according to this rule should be the exact [Rh 6 (CO) 15 11 - 54 32 86 108 11 Octahedron
one to permit the metal atoms to fill up all their valence orbitals (18 electrons per tr 6 (CO) 16 54 32 86 108 11 Octahedron
metal atom) .
Although this rule can be applied to individual atoms in a cluster, it is more ' Contribution of halides to electron counting: p,-X = 2 electrons, u2-X = 4 electrons and A3-X = 6
electrons.
satisfactory to consider the cluster as a whole. The total number of electrons in • H is considered to contribute with I electron .
the system corresponds to the sum of the metal valence electrons plus the • Cp = n5-C5 H 5 is considered to contribute with 5 electrons .


2 Transition Metal Cluster Chemistry 2.3 Bonding in Metal Clusters 95

94

. Relationship between structure and number of cluster valence electrons according to the
Table 2.10
18-electron rule

Metal cluster structure

No . of Cluster valence electrons

Triangle
48
Open triangle
50
Tetrahedron The rhenium halide anion [Re 3 X 12 ]` - with 42 electrons is also an
60
62
"Butterfly" electron-poor system . The principal characteristic of a series of tri and
Square pyramid
74 tetrarhenium clusters are shown in Table 2 .11 . The peculiarly short Re-Re
76 Trigonal bipyramid
Octahedron distances observed for the halide derivatives agree with the three Re-Re
86
double bonds predicted by the 18-electron rule .
3 . The electron excess regarding the magic numbers for a given structure implies
the rupture of bonds and cluster opening, so bonding orbitals are converted
many exceptions to the rule . Thus for instance, the existence of paramagnetic in non-bonding ones for housing the electron excess .
trinuclear species as C03(CO)9S and Ni 3 (CO) 2 (rr-Cp) 3 indicates the presence of
partially empty metal valence orbitals . The compound Co 3 (CO) 4(SEt), in
which the group SEt comports as 3-electron donor does not fulfil the require-
ments of the t8-electron rule either, because it has 50 electrons, more than the 48
electrons required for the nucleus Co 3 .
For hexanuclear clusters, deviations of the 18-electron rule are almost
systematic since these clusters normally have 86 electrons, i .e . two electrons
more than the required for an inert-gas shell configuration . As occurring in the clusters Re 4 (CO) 14 (tetrahedron, 60 electrons),
In spite of the apparent restrictions to the application of the 18-electron rule
[Re 4 (CO), 6 ] 2- (butterfly, 62 electrons), and Pt 4 (CH 3 CO 2 ) 8 or 0$4S(C0) 12 -
it is certainly interesting to discuss some of its consequences or corollaries : (CCHPh) (planar 64 electrons) (see Table 2 .3 and Fig. 2 .14), close and open
1 . There is a determined correspondence between the type of polyhedron built structures are related by differences of two electrons .
by metal-metal simple bonds and the number of electrons in the system .
There is a kind of magic numbers for building polyhedra . These numbers for M -M M M -M
some common polyhedra are given in Table 2 .10. Those clusters with an 2 e \ .2e
electron number higher or lower than the corresponding magic number are ~~\/' +- 2e ' / ~-2e
seen as electron-rich or electron-poor cluster respectively . M M M' / M I -M
2 . In the case of electron-poor systems the electron deficit must be compensated 60 electrons 62 electrons 64 electrons
by the formation of multiple bonds. Thus, the compound H 2 0s 3 (CO) 10 that
actually has only 46 electrons should have an Os-Os double bond leading to
2.3.2 Polyhedral Skeletal Electron Pair Theory
an isosceles triangular array of osmium atoms . Such a prediction agrees with
structural data (Table 2 .2) which show indeed one Os-Os distance of 2 .60 A,
The polyhedral skeletal electron pair approach retains the condition that each
shorter than the other two (2 .8 A) .
metal atom uses its nine valence atomic orbitals . However it does not consider
all the electron in the system but only those involved in the metal network . This
approach is fundamentally grounded on the analogy existing between metal
clusters and boron hydrides and carboranes .

48 electrons 46 electrons
Analogously, the Rhenium hydride H 4 Re4 (CO) 12 with 56 electrons is also
an unsaturated species. Two double bonds delocalized in a tetrahedral
structure as shown in following resonance structures should agree with the
relatively symmetric structure found for that compound (see Table 2 .3).
Bonding in Boranes and Carboranes . Although in Chapter 4 some aspects of the
boron cluster chemistry will be considered, it is convenient to discuss here some
structure and bonding features characteristic for boron clusters .
Boron hydrides and carboranes adopt structures in which their skeletal
boron and/or carbon atoms form complete or nearly complete deltahedra, i.e .
regular polyhedra with triangular faces .


Table 2 .11. Correlation between metal polyhedron geometry and cluster valence electron counting.

`ir
Structural properties of selected rhenium clusters

Compound Polyhedron Distance% Type of Ligands Number Ref.

geometry Re-Re (d) Re-Re bridging of valence
bonding Re- Re bonds electrons
a b c
Metal -- 2 .75
Re 3 C1 9 Equilateral
triangle 2 .49 Double p,-Cl 42 1
,.rbbl~
rfr
Equilateral Me
~~'I~
[Re3Cl, a ] 3
triangle 2 .47 Double le e-C1 42 2, 3
•
~~
Re 3G 3{CH2SiMc,)6 Equilateral
triangle 2.39 Double k2-Cl 42 4
,vW
[H4 Re 3(CO),a ] - Isosceles
triangle 3.18 Single 46 5 d e f
K2-H
282 Double bis(p 2 -H)

I
[H 3 Re 3(CO), o ] 2- Isosceles /~\\
triangle 3.03 Single one (le a -H) 46 6 /~' ~. ~~
for two bonds
2.80 Double bis (fe e -H) ~'~1~
14 //
[HRe3(CO)12] 2- Isosceles
triangle 3.01 Single 48 7 \~
3.12 Single u2-H 9 I1 ~
[H2 Re 3(CO), 2 ] - Isosceles
triangle 3 .18 Single p2-H 48 8 Fig . 217. Regular deltahedra often found in molecular structures of horanes and carboranes_ (a)
3 .04 Single Tetnthedron; (b) trigonal bipyramid ; Ic) octahedron ; (d) pentagonal bipyramid; (e) dodecahedron ; (f)
HRei(CO), 4 Bent. Angle 3 .29 Single p a -H 50 9 tricappcd trigonal prism ; (g) bicapped archimedean antiprism ; (h) octahedron (I) icosahedron
Re-Re-Re = 90`
H4Re4 (CO) 11 Tetrahedron 2.90-2 .95 Partially
double p 3 -H 56 10
[H 6 RejCO), 2 ] 2- Tetrahedron 3.14-3 .17 Single p 2 -H 60 11
[Re4(CO) 16 ] 2- Two fused 2.96-3 .02 Single 62 12 structures can be appreciated in Fig . 2.28 . In closo-structures, skeletal boron or
coplanar carbon atoms occupy all the vertexes of the polyhedron . In the case of nido- and
triangles arachno-structures one and two of the vertexes of the appropriate polyhedron
remain unoccupied respectively .
References
On each skeleton boron or carbon atom there is always a hydrogen atom or
1 Cotton FA, Mague IT (1964) Inorg . Chem . 3 : 1094 some other simple terminal ligand which emerges radially away from the center
2 Bertrand JA, Cotton FA, Dollase WA (1963) Inorg . Chem. 2 :1166
3 Robinson WT, Fergusson JE, Penfold BR (1963) Proc. Chem . Soc ., 116 of the polyhedron and that is linked to the cluster by a single two-electron bond.
4 Hursthouse MB, Malik KMA (1979) J . Chem . Soc., Dalton Trans, 1334 Therefore, the skeleton distracts two electrons per atom for such interactions .
5 Ciani G, D'Alfonso G. Freni M, Romiti P, Sironi A, Albinati A (1977) J . Organomet . Chem . The remaining valence-shell electrons are regarded as skeletal bonding elec-
136 : C49
6"Bertolucei G, Freni M, Romiti P, Ciani G, Sironi A, Albano VG (1976) J . Organomet. Chem . trons .
113 :C61 Each carbon or boron atom contributes with four orbitals . Due to the
7 Ciani G, D'Alfonso G, Freni M . Romiti P, Sironi A (1978) J . Organomet. Chem . 157 :199 pseudo-spherical surface of these atom polyhedra, a convenient hybridation for
8 Churchill MR, Bird PH, Kaesz HD, Bau R . Fontal B (1968) J . Am . Chem. Soc . 90 :7135
9 Teller RG, Bau R (1982) Struct . Bonding 44 : 1 the atomic orbitals of skeletal atoms should be, for instance, two radially
10 Bau R, Kirtley SW, Sorrell TN, Winarko S (1974)1. Am . Chem . Soc. 96 :998 oriented hybrid sp-orbitals and two pure p orbitals as shown schematically in
11 Ciani G, Sironi A, Albano VG (1977) J . Organomet. Chem . 136 :339 Fig . 2 .29 . If the outward pointing sp hybrid orbitals are assigned to the linkages
12 Churchill MR, Bau R lnorg . Chem . 7 :2606
with the radial ligands, three atomic orbitals on each boron or carbon atom
would remain available for the skeletal bonding . One of these orbitals is an
The structure of most known boranes and carboranes are based on the inward pointing, radially oriented sp hybrid orbital . The other two are p orbitals
regular deltahedra illustrated in Fig. 2 .27 . Three types of structures are known oriented tangentially at the cluster surface.
for this class of compounds : closo (closed), nido (nest-like) and arachno-struc- In a polyhedron of n vertices there are then 3n atomic orbitals available for
tunes ("cobweb" structures) . The relationship between these three types of the boron or boron-carbon skeleton . These orbitals may be then linearly


2 Transition Metal Cluster Chemistry 2.3 Bonding in Metal Clusters 99

98

CLOSO N IDO ARACHNO Fig . 2 .29• Hybrid orbitals of boron useful in bonding desorip-
A 4 tion of boranes and carboranes

6 !;~!
\Y ,
API

1fP0 i
// w A
s +
=
9 T
Show

atg t 2g t lu

11

12
,,y,,29 ' l
ti . ,t2 u a
12 it F
TASO's
Fig. 2.28. Closo, nido and arachno boranes. Reproduced with permission from Rudolph RW, t'
b
Pretzer WR (1972) Inorg . Chem. 1l1 : 197 ~~:~ tut~ln}
(LUMO)

Or Ar)
Gig' t lu•eg (HOMO)
6a
combined to a set of 3n molecular orbitals arranged according to the symmetry t TASO's t29(7r)
properties of the cluster . Of these 3n skeleton molecular orbitals, (n + 1) are a lg (o)
bonding orbitals . Figure 2.3© describes schematically the linear combinations
generating the skeleton bonding molecular orbitals in the octahedral cluster -
6 BH (13H) 2
anion [B 6 H 6] 2- . There, the six BH groups are linearly combined to give seven 6
bonding molecular orbitals. An unique orbital of symmetry a t9 arises from the Fig. 2 .30. Linear atomic orbital combinations giving rise to skeleton bonding molecular orbitals in
combination in phase of the six radial sp atomic orbitals . The interaction of the the anion [%9H6]1 . (a) Orbital sketches; (b) qualitative Molecular Orbital energy diagram

100 2 Transition Metal Cluster Chemistry
12 tangentially oriented p orbitals lead on the other side to two sets of triple
degenerated bonding molecular orbitals of symmetry t2 g and t2u .
The same molecular orbital distribution pattern persists for higher borane
anions [B„ H n ] 2 - . There are always (n + 1) bonding molecular orbitals, one of
at or ag symmetry representing the in phase combination of the radially oriented
sp hybrid atomic orbitals but without contribution of the tangentially oriented
p orbitals . The remaining n bonding molecular orbitals arising from the inter-
action of the 2n tangentially oriented p atomic orbitals are therefore primarily
polyhedron surface orbitals .
Since the number of bonding molecular orbitals is determined by the cluster
symmetry, the same polyhedron can serve as the basis for the structures of
an ample range of isoelectronic species as neutral carboranes with formula
C2B„_ 2H„ or the naked clusters as Ge9 - that will be dealt with in Chapter 4.
Formally, neutral nido and arachno-boranes with general formula B„H n+4
and B,,H„ t 6 are related with the hypothetical anions [B„Hj4 - and
[B,,Hn]6- . The anion [B,;H .] 4 ' contains n + 2 skeletal electron pairs (one from
each BH unit plus anion charge) . The nido-species related to this hypothetical
anion contain therefore a number of electrons appropriate for an arrangement
of their n skeletal atoms in an (n + 1)-vertex polyhedron in which one vertex is
left vacant . Analogously, the arachno-species formally related to the anion
[BnHn] 6- contain n + 3 skeleton electron pairs which are appropriate for
a polyhedron with n + 2 vertices in which two of the vertices are left vacant .
In the neutral nido-boranes B,,H i+4 , corresponding to the addition of four metal electrons . In the case of species with n-acceptor ligands all these six metal
protons to the anion [B„H„]4-, the extra hydrogens occupy BHB bridging orbitals are stabilized by metal-ligand interactions . Some of them accepting
positions preserving the symmetry of the system to a great extent . Analogously
in the B„H i+6 arachno-boranes the six extra hydrogen atoms occupy endo-
terminal BH or bridging BHB positions .
Transition Metal Clusters . For the application of the skeletal electron pair
theory deduced from the structural properties of boranes and carboranes to
transitions metal clusters, it is necessary to establish some assumptions :
1 . Each transition metal in the cluster uses its nine atomic orbitals . However
only three of them effectively contribute to form the metal skeleton . The
remaining six orbitals are available for bonding with the ligands and for
housing non-bonding electron pairs .
2. The three atomic orbitals per metal compromised in the metal skeleton have
a form and a symmetry similar to those of the sp hybrid atomic orbital and
tangential p orbitals in the corresponding boranes and carboranes .
Under such assumptions metal ions should behave as quasi-main group
elements and the probable cluster shape may be then derived from the number
of electron pairs available for the cluster bonding . The correspondence between Electron Pair Theory is to regard the cluster as being made up of a group of
number of bonding skeletal electron pairs and geometry of metal polyhedra is
shown in Table 2.12.
2.3 Bonding in Metal Clusters 101
Table 2.12. Correlation between metal polyhedron geometry and the number of skeletal electron
pairs
Number of skeletal electron pairs Fundamental metal polyhedron
7 Octahed bipyramid
Octahedron
8 Pentagonal bipyramid
9 Dodecahedron
10
11
Tricapped trigonal prism
Bicapped square antiprism
12 Octadecahedron
13 Icosahedron
A convenient procedure for electron counting in metal clusters is achieved by
making a balance between the number of electrons in the system and the atomic
orbitals to which they can be assigned .
The total number of electrons associated with the valence shell of cluster
metal atoms corresponds to the sum of the metal valence electrons, v, plus those
provided by the ligands, L .
As mentioned already, from the nine orbitals provided by each transition
metal atom, three are left to form the metal skeleton . The remaining six orbitals
are to be used in the metal-ligand bonds as well as for housing non-bonding
electron density of the a-donor ligands and the others by back-donation
towards empty a-acceptor orbitals in the ligands . Accordingly, in the distribu-
tion of the cluster valence-electrons, these six orbitals will be filled preferentially .
Thus, each transition metal atom in the cluster will always spend twelve
electrons for accommodating ligands and non-bonding electrons furnishing
(v + 2L - 12) electrons for skeletal bonding .
The same procedure is also valid for mixed clusters containing both
transition metals and main group elements. Each main group element will leave
three atomic orbitals available for cluster bonding and one remaining valence-
shell atomic orbital either to accommodate a lone pair or to bond a suitable
! ligand . The number of electrons supplied by one atom E or group EL for cluster
i is (v + y - 2) where v is the number of valence shell of the cluster atom E and
y the number of electrons furnished by the ligand L . Table 2.13 summarizes the
electron contribution of a some main group cluster units.
A number of applications of these electron counting procedure are ilius-
trated in Table 2.14.
An alternative procedure for counting electrons according to the Skeleton
fragments. Thus Os s(CO) 16 may be considered as a combination of five
Os(CO)3 fragments and an additional CO-ligand . By the same arguments


2 .3 Bonding in Metal Clusters 103

102 2 Transition Metal Cluster Chemistry

Table 2.13. The number of skeletal bonding electrons contributed by some main group cluster Table 115. The number of skeletal bonding electrons contributed by selected organo transition
fragments' metal fragments

Main group element E EH EH 2 or EL Fe(CO) Co(CO) Ni(CO)

(X = 0) (X = 1) (X = 2) - 2 - 1 0
Fe(CO) 2 Co(CO) Z Ni(CO) :
3 B, Al . Ga. In, T) 1 2 3 0 1 2
4 C, Si, Ge, Sri, Pb 2 3 4 Cr(CO)3 Mn(CO), Fe(CO)3 Co(CO)3 Ni(( - O),
N, P, As, Sb, Bi 3 4 5 0 1 2 3 4
5
6 O, S, Si . Te 4 5 6 V(CO) 4 Cr(CO) 4 Mn(CO) 4 Fe(CO), Co(CO) 4
7 F, Cl, Br, 1 5 [6] [7] t 2 3 4 5
Mn(rr-Cp) Fe(n-Cp) Co(n-Cp) Ni(,r-Cp)
0 1 2 3
" No. of skeletal electrons = v + X - 2 where r is the number of valence shell electrons on the main
group element E and X is the number of electrons from ligand(s) on E .
Reference
Reference
Wade K (1975) Chem . Br . 11 : 177 Mingos IMP (1972) Nature Phys. Sci . 236 :99

2 . Skeletal electron counting_ Examples and applications

Table .14 skeletal electron pairs for the m + I (m = 5) available skeletal orbitals in
a trigonal bipyramide metal arrangement .
Compound Cluster Ligand and Skeleton Cluster structure
valence non-bonding electron Table 2 .15 summarizes the number of electrons contributed by a variety of
electrons electrons pairs common organometallie fragments .
OS 5 (CO) 16 72 60 6 Trigonal bipyramid
[B 5 H 5 ] 2- 22 t0 6 Trigonal bipyramid
Fe 3 Bi 2 (CO) 12 52 40 6 Trigonal bipyramid 2.3.3 Isolobal Relationships
Pbs - 22 10 6 Trigonal bipyramid
[Mo6C1 14 ] 2 86 72 7 Octahedron The basis of the Skeleton Electron Pair Theory described above rest on the
Co 6(CO) 16 86 72 7 Octahedron assumption that the constituent fragments of main group and transition metal
C,B4 H 6 26 12 7 Octahedron
Co,B 3H 5 (Cp)3 56 42 7 Octahedron clusters contribute both the same number of electrons and orbitals for the
FeB 4C 2 H 6(CO) 3 40 24 8 Pentagonal bipyramid cluster bonding and that these orbitals have similar nodal properties .
[B,H,] 2- 30 14 8 Pentagonal bipyramid Semiempirical molecular orbital analyses of the frontier molecular orbitals
B 6C2H e 34 16 9 D2d-Dodecahedron of metal carbonyl fragments confirm that there are definite similarities between
[Ni g(CO) 1e ] 2- 128 108 to Stacked trigonal prism the numbers, energies, shapes and nodal characteristics of these orbitals and
B,C2 H 9 38 18 10 Tricapped trigonal prism
[Mn13 6C 7.H 5 (CO) 3] - 48 28 10 Tricapped trigonal prism those in main group fragments . Fig . 2 .31 illustrates qualitative orbital descrip-
Pby - 38 16 11 Capped square antiprism tions of three pair of fragments . Similarity between the fragments is apparent .
B H 9S 40 18 11 Capped square antiprism Although they are neither isostructural nor isoelectronic each one of them has
Os 5(CO), 6 72 60 6 Trigonal bipyramid a frontier orbital which is approximately equivalent . When this kind of situation
Ni3B5CH6(Cp)3 70 48 11 Capped square antiprism
&,C2 H 11 occurs -in which the number, symmetry properties, approximate energy and
46 22 12 Octadecahedron
CoB5 C2 H, 0 Cp 56 32 12 Octadecahedron shape of the frontier orbitals, and the number of electrons are similar - they are
Co2B 5 C 2 H 1C,(Cp) 2 70 44 13 Icosahedron said to be isolobal fragments and are symbolized with a double arrow as
indicated at the bottom of the schemes in Fig . 2 .31 . In Table 2.16 is summarized
a series of isolobal relationships between a variety of main group and transition
discussed above the number of electrons contributed by each M(CO), fragment organometallic fragments .
for skeletal bonding in the cluster is (v + 2x - 12) where v is the number of Some more rigorous, non-parametric calculations also confirm the validity
valence electrons of the metal M . of the isolobal principle . Fenske-Hall LCAO-MO-SCF calculations of the
Since each unit in Os 5 (CO) 16 contributes with two electrons structure of B S H 9 and some of its ferroborane derivatives, i .e. 1-Fe(CO) 3 B 4H a ,
[8 + (2 x 3) - 12], the five units plus the additional two electrons of the co- 2-Fe(CO) 3 B4 H a and 1,2-[Fe(CO) 3 ] 2 B 3 H 3 have been completed . A summary
group give a total of 12 electrons for the skeletal bonding . Thus there are six of a qualitative description of the properties of frontier molecular orbitals in


104 2 Transitin Metal Cluster Chemistry 2.3 Bnding in Metal Clusters 105

Table .16
2 . Examples f islbal fragment relatinships'

CH 3 CH, CH

.~ d al e f+ ~@ H p2-S
EL 3 (E - P, As)
al t P Mn(CO) 5 Fe (CO)4 C(CO),
a b2*
Ni(Cp)
* 1 b2 * al Fe(CO)2(Cp) Rh(CO) (Cp*)
M(CO), (Cp) Rc(CO)2(Cp) W (CO) 2 (Cp)
[Mn(CO)2(Cp)]'
129 . 40
Cr(CO) (NO) (Cp)
C(CO)4 Cr(CO) 5 Re(CO)4
- Rh(,1 6 -C 6 H,)
; Zn(Cp) Cu(Cp*)
2g Au(PPh 3 ) Ira(CO)2 ReICO) 3 Br 2
d 9-ML 3 - p CR Fe(CO)4- 3 -CH2 Rh(PPh,)2(,j`-C_B„H,,) Fe(CO)2(ri'-C2B9HI,) Mn(CO)(h 5-C ZB 9 H,,)
TaMc(Cp) 2 TaCI(PMe 3 ) 2 (Cp)
0 b
CH, CH= CH'

Cr(CO), Mn(CO) 4 Fe(CO)3

Mn(CO)2 (Cp) Fe(CO) (Cp) Rh(Cp)
BH 3 BH 2 OH

islbal crrelatins are nt ne-t-ne relatinships, s a given fragment may be islbal with
mre than ne ther fragment .

References
Stne FGA (1984) Angew . Chem . 96 :85
Mings DM P, Jhnstn RL (1987) Struct . Bnding 68 :31
d 7-ML3 --T- CH 3
C

B5H9 1 - Fe(CO) 3 B4 He
Fig . 231 . Islhal relatinships f selected fragments [Hffmann R (1982) Angew . Chem . 94 . 725]

C 5 H 9 and 1-Fe(CO),B 4H g can be bserved in Fig . 2 .32 . The HOMO-I and

HOMO-2 f B 5 H9 are an e and an a t rbital respectively . Bth f these rbitals
are invlved in cluster bnding between the apical brn atm and the basal
B4 H 8 grup . The a t rbital als cntains significant (BH)-apical character . The e--
-14
electrnic structure f 1-Fe(CO) 3 B4 H 8 is very similar in terms f the cluster a
e and a t rbitals . In additin there are three nn-bnding rbitals that are t-
predminantly lcalized n Fe(CO) 3 ("d 6 "). CD
The shape and ndal characteristics f the e and a t rbitals in bth MO -16 a,-
cmplexes bserved in the cntur diagrams reprduced in Fig. 2 .33 prvide
a mre quantitative assessment f the islbal principle fr these cmpunds . Fig . 2 .32. Qualitative descriptin f upper MOs in B 3 H 9 and 1-Fe(('O) 3B4 H5 . Reprduced with
The islbal principle is widely appreciated as ne f the mst valuable • permissin frm DeKck RL, Fehlner TP (1982) Plyhedrn 1 : 521
generalizatins in mdern inrganic chemistry . Amng numerus applicatins
f the islbal arguments t clusters is the ratinalizatin f the transitin metal
cluster gemetries by identifying islbal fragments . These arguments are als l amic aspects f the prblem can lead t deviatins in the predictins based n
cnsiderably useful as a tl fr designing synthetic pathways fr cluster species . the islbal principle .
The islbal principle whlly arises frm cnsideratins abut the electrnic Finally, it shuld be remembered that the rbitals f islbal fragments are
structure f mlecular fragments at a micrscpic level . Kinetic and thermdyn- frequently nn identical . There are differences, specially between fragments


106 2 Transition Metal Cluster Chemistry 2.3 Bonding in Metal Clusters 107

The Capping Principle has been derived for evaluating the electron count in
condensed polyhedra from those of its component polyhedra . Thus, it has been
established that the total electron count in a condensed polyhedron is equal to
the sum of the electron count for the parent polyhedron minus the electron count
characteristic of the atom, pairs of atoms, or face of atoms which are common to
both polyhedra . The frontier orbitals of the capping fragment are matched in

closo 2e
-1 - n ;do -12 e . arachno

e orbital
OCTAHrnPON
"k 186e) ~0 t7r,el t62e1
l0$6([00
(101
1 0 0, SC [C 01, S j0%N[CC1l,j

•'
12e

WAN. \

MONO-CAP MA

05,1(0121 H7Os 6 1C01 t 8 HZOSS)C01t6

12e 198e) 186el 1716 e1

H H
/, .
near,
BI • CAP .
a,orbilal . .
10s 8 t(0)22) 2- not observed - Os 6fC01 1B1py1 •'
Fig. 2.33 . Orbital contour diagrams for molecular orbitals e and a t of B S H9 and Fe(CO),B ' H 5 . 1110e) (98e1 1616e)
Reproduced with permission from DeKock RL and Fehlner TP (1982) Polyhedron L 521 12e .

. A0" M .A\ •
tar-(AP
\./
constituted by main group elements and by transition metals in which the
d-electrons always play an important role that may have chemical significance
affecting the applicability of the principle . (112,1 1110et 198e1
not observed not observed "20571(01 70
12e

2.3.4 Capping Principle 4 n

The polyhedral Skeletal Electron Pair Theory as described above is particularly TETRA-CAP
I
effective for rationalizing the structures of the species which adopt spherical
`/f134e1 a 11770 t+s 0,1
deltahedral geometries or fragments derived from them as being the nido and
arachno geometries . However, only a limited number of large clusters adopt as ros,oci(o12~1 2- fOs 9 lc o11 ,a~ n, 5 I20e 1HOc 8I( 0t 22t

their structure polyhedra of this type and they are often structurally better
Fig. 2.34. Application of the decapping and capping principles to osmium carbonyl clusters .
described in terms of condensed polyhedra derived from triangular, tetrahedral, Reproduced with permission from Mingos DMA . May AS (1990) In : Shriver DF, Kaesz HD, Adams
trigonal prismatic, and octahedral components (see Figs . 2 .25 and 2 .26). RD (eds), The chemistry of metal cluster complexes . VCH . New York, p I1


108 2 Transition Metal Cluster Chemistry 2.3 Bonding in Metal Clusters 109

symmetry by orbitals of the parent clusters which are already bondig, so no

changes in the number of skeletal bondig molecular orbitals result from the c o
capping process. c='Y 0O ? 7 00 O^ O r -'
-J`ON7 N~ O0000 •O
.O IC 7
~r 10 7 N rJ C 7 00 7 %O N N
NM[~7r+ NNr N~~)
z > y rn
Consequently, capping with a conical M(CO) 3 fragment with twelve elc-
trons in non-bondig and metal-ligand bondig orbitals (isolobal for instance
with a CH-group) leads to an increase in cluster valenc elctron count of twelve . E
N
L
Thus, capped deltahedral clusters are characterized by [(l4n + 2) + 12m] val- a

enc elctrons, where n is the number of metal atoms in the parent deltahedron
and m is the number of capping conical metal fragments. r E v b C
E E ~~ aE
A classical example of correlation of structure with valenc elctron count is 1

shown in Fi.g 2.34. There the structures of a series of osmium clusters are N t, U
E C, 14 C R Y N G O L
,S h= a 05LS %
systematized by using the capping principle combined with the approach of v -M Z
.L IT, on
U v
3
c V '
r N y' ~' :J r U O' V O u 7
decapping (i.e. removal of cluster vertices). CA OF(n F-of-t-F OOv-r. O !F-m~! aN a~mv3.
As mentioned in Sect. 2.2. there are also ring and planar raft metal clusters .
Many of them may be considered to be derived from the fragment ML4 which
inde fr_4 UCII ly appears as ge- an ri
edb dgin fragment . The tendecy of this °'E V
fragment to adopt this type of bondig may be understood bearing in mind that c 0
the fragment d'-ML, is isolobal with the unit CH 2 (see Fig. 2 .31b). CL
The fragment Os(CO) 4 has, for instance, 14 elctrons in non-bondig and y o
metal-ligand bondig orbitals . Bridgin the edgs of a given cluster with m c
of these groups leads therefore to an increase in the skeleton elctrons C.
a C
of 14m . Hence edg-bridge deltahedra are in genral characterized by o a . =~ .,
v o =
[(24n + 2) + 14m] elctrons . . • .
0 L C) 5i
uu ~O ~z°
E E q ti v a y O' a O r r oil rs ~m x h a
C U n (L [L a U .`. oe - U ac v PG
233 Rules for Cluster Structure-Electron Counting Correlations oC,

The relationships between structure and elctron counting discussed above are o Q
• h= At C-
valid for a great number of both main group and transition metal cluster ro
7
.c rY ON
N
G '? ,^.
•
*. M r V + +h
compounds where the indvidual atoms conform to the noble-gas rule. Such E E O +~ +O
+ CAI + CAI
°n • C + CAI
correlations have ben summarized in form of a series of specif rules that have 'g U. C 7 v C d C a C
proved to be applicable to the majority of cluster compounds . These set of rules o
are listed in Table 2 .17 . ,
q •
7 C _ N 7 .O
% v .d + + +
c E ~ .- C C C

23 .6 Platinum and Gold Clusters '~ Y

C C
• d Q U ; r cp
•
ro u^ - °~N o 0
v OH O ` .?~'~ C v + 7+ `~+
Platinum clusters genrally do not agre with the elctronic requiremnts of 2
transitions metal clusters established by the polyhedral Skeletal Electron Pair
• v 0 O .V, L' r' Y R L C F .D O
Theory . These clusters genrally possess fewer elctrons than expected from this
I> '
N
theory .
The elctron count in a series of platinum clusters can be seen in Table 2.18 . U (~ V V !7 Y ' N V C r" V Cj V Pj V j
C u i b _• h
OL G C ^ ro
• ~" C YN pro„
v^ d V L ro C
V d ^
The reason why that occurs appears to be the hig enrgy of the atomic N f -' t> C v 3 O s v E U v r
P.-orbital . The molecular orbitals derived from this orbital perpendicular to the a '~ ?. ~u > u

metal-ligand plane are also hig-lying and unavailable for bondig . F ^ N a



2.3 Bonding in Metal Clusters ill

110 2 Transition Metal Cluster Chemistry

Table 2.18. Electron counting in platinum cluster compounds

Skeletal geometry Platinum cluster Electron count

Triangle Pt 3(CO)3( PR3 ) ; 42

Tetrahedron Pt4(PR 3 )4H s 56
0 Butterfly Pt 4(CO)s(PR 3 )4 58
+ o .E o Triagonal pyramid Pt s(PR 3 )3 H 8 68
ao E
+ 2 s i k d Edge-bridged tetrahedron Pt s(CO)6(PR3 )4 70
+ T My w 't"., 7~ + Triagonal prism [Pt6(CO), 2 ] 2- 90
COaU
C
• d L
Reference
V
R f U Mingos DMP, Wardle RWM (1985) Transition Met . Chem . 10 :441
U
d
O m .,.coot- 0 OW U~S ?Up
E
0
U
V
d
s
The high effective nuclear charge experienced by d electrons in the elements
U
of the group 11 or coinage metals causes them to be contracted and low-lying .
Hence the d 10 shell in gold clusters practically does not contribute to metal-
E
metal bonding . Moreover, and by the same reason, the s-p promotion energy is
very large and the valence p orbitals have a diminished role in cluster bonding .
Nonetheless there are a great number of clusters containing AuL fragments. The
U
Au(PR 3 ) fragment, which appears to have a low-lying sp hybrid orbital with
.0 high s-character and two empty p orbitals, is indeed isolobal among others with
l-
.
0 n
H, CH 3 , or Co(CO) 4. Accordingly, Au(PR 3) is often found capping triangular
T
E • L faces in deltahedra or bridging edges in various types of clusters .
w • 0 In gold clusters of the type [Au,„(PR3)m]', as the triphenyl phosphine
x
E derivatives shown schematically in Fig . 2.35, the electron count depends critic-
ally on both the nuclearity and geometry of the species .
U N
0 In high nuclearity gold clusters with the general formula
O ~,+M a
A N
E i
[Au (Au(PR3)}m]"+, which are found in the two types of topologies exemplified
r "T
.G ~
R 3
wen
in Fig. 2.36, not only the s gold orbitals but the p orbitals are also used for cluster
OV- U
.O 0a + U +
a 'p 0 bonding .
•E
L a • A as -8
`a
L U T
£ P y a
• • ' .:+ n
0 0
E=^0 w
a
U C C
C 71 O V O 0
w
a M U n
R
i. 00
U
O •• ^~
_a c
0 0
•
.n ~ to
• C.
•
• 3 O a U
A
V O
•
U y L s- !0,
V RS O
H
y ~ 0 `~ V
V (y
y P
oai0 ^v-~~ E 6s G A .c a b c
•
N
00 J A y
00 to I
Fig . 2.35a-c . Schematic structures of gold clusters. (a) Au4 1 2 (PPh3 )4 ; (b) [Au b(PPh3)b ] 2 ' : (c)
a (Aui(PPh3)7] +


11  Transition Metal Cluster Chemistry . Bonding in Metal Clusters 11

Fig.  .6. Examples or high nuclearity gold clusters (a)

mo&
Fig. .& Model for molecular cluster
Metal nucleus in the clusters [Au(Au„Cl,(PR,),o]' ; M  ,(PR,)  . Reproduced with permission
(b) [Au(Au,CI,PR,),,]' from G . Schmid (1985) Struct . Bonding
9
,=
6 :5

AP
a b

• 0 o
• • Fig. .7. Schemes of polyaurated species
with five and six gold atoms . X = C or N ;
Y = PPh, [Schidbaur H (1990) Gold Bull .
• •  :11]

In recent developments of gold chemistry, an unexpected affinity between

gold atoms, even with closed shell electronic configurations and equivalent ~' 4 \
electrical charges, has been observed . In such a context the term "aurophilicity"
has been mentioned. According to this concept, gold atoms show a pronounced
tendency to cluster around a given central element . Thus pyramidal species J MINIM . Of
[E(AuL)  ] + with E = 0, S, or Se show short Au-Au distances . A number of
polyaurated species as those shown in the schemes in Fig .  .7 have been indeed 0
isolated .
i

..7 Large Clusters

Gold phosphine compounds have also played a major role in the synthesis of
exceptional large or "giant" clusters . From the reduction of PhAuCl with
diborane, the compound Au 5S (PPh  ) 1 C1 6 can be obtained . This stoichiometry
verified by analytical and molecular weight determinations is explained as an
Au 1-nucleus surrounded by Au-atoms coordinated by phosphine ligands
giving thus an arrangement of close-packed gold atoms . The Mossbauer spec-
trum of the compound shows indeed four different types of gold atoms, i .e.
atoms in the nucleus, atoms coordinated to phosphine and to chloride ions, and
also uncoordinated surface gold . Similar M55 clusters of rhodium, ruthenium,
and platinum have also been isolated . Figure  .8 reproduces a schematically
representation of these type of clusters . According to NMR studies, ligands on
the cluster surface are mobile and change their positions very fast . Mobility of
cluster surface atoms can be also deduced from such experiments . Consequently
a b
Fig. .9. Sideviews of metal framework of clusters (a) (p-Tol,P),  Au, 5 Ag 0Cl„ and (b)
[(p - Tol,P)„Au 18 Ag, 5 Br11] + . Reproduced with permission from Teo, BK (1988) Polyhedron
7 :17
a liquid-like behavior of the surface atoms appears to be one of the peculiar
physical properties of such large clusters . It is very probable that this character-
istic behavior of these giant clusters prevents the formation of the material
required for crystallographic structure determinations .
Among large metal clusters there are also some heteronuclear or mixed-
metal clusters that have been mentioned as "metal-alloy clusters" . The bimetallic
Au-Ag clusters (P-TolP)rAuisAgoCi1e and [(P-TolP)tzAulaAg9Brtt] z+,
whose metal frameworks are illustrated in Fig . .9, belong to this class . A very

114 2 Transition Metal Cluster Chemistry
m)
ill
am
40 Au
~~ • C> A g
~~ • • combination of the 54 metal valence atomic orbitals to groups of molecular
~•
s e S
a b
Fig. 240. Schematic representation of metal framework of cluster . (p-T0I 3P) 12 Au t5 Ag 20C1 14 as
three-edge-sharing icosahedra . Reproduced with permission from Teo, BK (1988) Polyhedron
7 :2317
interesting structural feature in these clusters is that they can be considered as
being formed by 13-atom centered icosahedral cluster units . As shown in the
scheme reproduced in Fig . 2 .40, the 38-atom cluster may be described as three
icosahedra sharing three vertices plus two capping atoms . That has been
mentioned as an example of a possible building up principle for large clusters
based on the idea of "a cluster of clusters" .
Electron counting rules available for small and medium-sized clusters
appear to be insufficient for very large clusters with coordinatively unsaturated
surfaces. These types of clusters could be considered to be actually half way
between complexes and metals.
23.8 Quantitative Approaches to Delocalized Cluster Bonding Models
The analogy between boranes and carboranes and transition metal clusters rests
on the assumption that the fragments M(CO)x as well as the fragments BH in the
boron derivatives contribute with three orbitals to the formation of the metal
polyhedron . This analogy between electron-deficient boron species and the
electron-rich metal clusters is fundamentally empiric . However there are some
theoretical calculations for specific cluster species that make some clarity about
the degree of validity of such an analogy .
The nature of metal cluster networks is to some extent like that existing in
bulk metals with a high degree of electron delocalization . Molecular orbital
treatments are more appropriate for the description of such kinds of systems .
However detailed calculations including the cluster metal atoms as well as those
of the ligands are rather complex and expensive even for high symmetry systems .
Accordingly, many approaches frequently consider in a first approximation only
the valence atomic orbitals of skeletal metal atoms . That is equivalent to
considering an isolated bare cluster . Thereafter the metal-ligand interactions can
2 .3 Bonding in Metal Clusters Its
be taken into account by selecting those cluster molecular orbitals energetical
and symmetrically better disposed for these interactions . Such an approach is
consistent with the idea of a cluster as an independent entity .
Rather rigorous calculations have been made for the anion [C0 6 (CO)14] 4- .
The energies as well as the symmetries of the moleculs ar orbitalarising from
calculations for the isolated cluster Cob are reproduced in Table 2 .19a . From the
orbitals arise : 31 which can be considered as bonding or weakly bonding
orbitals and 23 which have a strongly antibonding nature . From the interaction
of the metal cluster molecular orbitals with the CO-ligands - with symmetries
a lg , e9 and tl,, for terminal CO groups and a,,, a 25 , tl,, and t2 9 for the
i z-bridging CO-groups-the molecular orbital scheme reproduced in Table
2.19b arises. According to this scheme, the 86 cluster valence electrons-58 from
the cobalt atoms and 28 from the donor CO-ligands -occupy 14 a'-metal-
carbon MOs and 29 bonding or weakly non-bonding cluster MOs . Therefore,
the external orbitals of the closed-shell electronic configuration of this cluster
are
.(1)]6 [ A 29 ]2 .
[7-2 .(2)]6 [T,
The HOMO as well as the LUMO in this cluster have metallic character .
The HOMO-LUMO gap is about 8000© cm - ', so a configuration with more
than 86 electrons would be rather unstable .
The fundamental assumption in the boranes and carboranes-metal clusters
analogy that considers each unit of the cluster contributing only three s-p hybrid
orbitals to form the metal cluster skeleton appears to be not totally confirmed
by the theoretical treatment analyzed above. This shows that is not possible to
define a precise set of molecular orbitals involved exclusively with the bonding
in the metal network . However, the number and the symmetry of the antibond-
ing molecular orbitals in [C06(CO)14] 4- (11 orbitals with symmetries T15, T2 .,
T lg and E g) with a strong s-p character are qualitatively analogous with the
equivalent orbitals calculated for the anion [B 6 H 6] 2- .
A somewhat more general theoretical treatment of metal cluster has been
performed through extended Hiickel calculations on a series of isolated rhodium
clusters with different geometries . Although the parameters (internuclear distan-
ces and AOs energies) used in such studies were always those from rhodium
species, their results depend mainly on the symmetry and shape of the AOs being
less sensitive to the parameters . The MO energy diagrams obtained from such
calculations are therefore to be considered as characteristic for the correspond-
ing geometries and able to be extended to other metal clusters .
According to these calculations, cluster MOs may be in general classified
into two groups: 1 . Valence-MOs, i .e . low-energy MOs containing metal elec-
trons or functioning as acceptors for donor ligand electron pairs and 2 . Anti-
bonding orbitals, i .e. high-energy MOs in general not able to either hold
non-bonding electrons or match ligand donor orbitals . The number of the
orbitals in each group (1) or (2) depends fundamentally on the geometry of the


116 2 Transition Metal Cluster Chemistry 2.3 Bonding in Metal Clusters 117

system . In very compact arrays where the interactions among atomic orbitals
Table 2.19. (A) Molecular orbital energies for the octahedral cluster Co
b and (B) a qualitative are strong, the relative number of high-energy molecular orbitals increases, thus
MO-scheme for the cluster anion [Co 6(CO) 14 ] - decreasing the number of electrons in the system . That occurs for example in the
case of the electron-deficient compounds and pure metals, the latter being
(A) (B)
Isolated Co b cluster a limiting case .
The [Co 61CO) 14 ] - anion
In Fig . 2 .41 the orbital interaction diagram for the bare cluster M 3 may be
Orbital Energy Cluster Metal-ligand Comments
observed . The 37 atomic orbitals of the three metal atoms give rise to 27
type orbital type orbital type molecular orbitals which can be classified in the groups (1) and (2) mentioned
above . Orbitals with symmetry e" and a 2 ' are strongly unstabilized and have an
E,(4) 3.3579 E,(4) antibonding character . The energy of these orbitals is significantly higher than
T, .(5) 2 .1404 T, .(5) that of the p orbitals in the free atoms, so it can be assumed they are normally
T,,(2) 1 .8640 Tl ,(2)
Antibonding vacant orbitals . Thus, a three-atom cluster has only 24 MOs to be used for both
cluster MO's
accepting ligand electron pairs and housing non-bonding electrons up to a total
T,(3) 1)1614 T2,(3)
of 48 electrons . Analogously to mononuclear compounds in which the metal has
T1 , (4) -0.2241 the tendency to have 18 valence-electrons, the cluster nucleus M 3 tend to reach
A, .(3)", Tl .(4)*,
A,,(3) -0.3163 E,(3)'°
48 electrons . As can be observed on Fig . 2.42, some of the metal AOs match
Antibonding
ligand orbitals of the same symmetry leading to normal bonding and antibond-
E,(3) -0.5065 A,,(1)', T24(3)', metal ligand MO's
• ing AO-combinations . In the case of M 3 (CO) r2 all cluster valence-MOs are
T2 r (3) -0.4609 A 2 i r,,(3)*
occupied ; 12 of them combined with CO orbitals and 12 remain unaltered
T,,(3)
containing 24 non-bonding electrons . It should be stressed that HOMO as well
-0.7271
A2, -0.9356 Az,
as LUMO have mainly metallic character .
T,,(1) -0.9430 TT .{1)
In general, it is then valid to say that a cluster of three metal atoms with any
T2. (2) -0 .9530 T2.(2)
given number of d-electrons will bond to the number of ligands necessary to
E,(2) E r (2)
reach a 48-electron configuration . However in certain clusters of the nickel
-0 .9565
E. -0.9691 E. Bonding and group, specially platinum derivatives, an additional high-lying e" orbital set
T2,(2) -0.9874 Tz .(2) weakly antibonding remains vacant and 44-electron clusters result instead . This is perhaps not
T, .(2) -0-9908 T, .(2) cluster MOs surprising since, as commented previously, platinum is known to form many
7'2.(1) - 1 .0167 T2 . 0 ) mononuclear square-planar 16-electron complexes .
E,(l) - 1 .0344 E,(I)
T1 .(1) - 1 .0411 TI .(1)

A2 . - 1 .0510
A,,(2) - 1 .0439 A 1 , (2)
T2,0) - 1 .0523 T24 (1)
A,,(1) - 1 .0857
A,,(3), Ti .(4)
E,(3) Bonding
metal ligand
A,,(1), T22(1), MOs
A 2., 71,(3)

' Energies in units of the metal d-valence orbital ionization energy .

Reference

Mingos DMP (1974) J . Chem. Soc., Dalton Trans ., 133 ~^ d block Fig. 2A1 . Orbital interaction diagram for a M 3 cluster. Re-
4d = = produced with permission from Lauher JW (1978) J . Am.
Chem. Sac . 100 :5305


118 2 Transition Metal Cluster Chemistry 2.3 Bonding in Metal Clusters l19

Table 2.20. Bonding capabilities of transition metal clusters estimated from extended Hjickel
calculations of the isolated metal clusters

Cluster Atoms Atomic High laying Cluster Cluster Examples

geometry (N) orbitals antibonding valence valence
(9N) orbitals molecular electrons
orbitals

Trimer 3 27 3 24 48 Os3 (CO)12

Tetrahedron 4 36 6 30 60 Rh4 (Co) 12
"Butterfly" 4 36 5 31 62 [Rh 4(CO) 15 ] 2-
Square plane 4 36 4 32 64 Pt4(MeCO 2 )$

Q\ '
Triagonal pyramid 5 45 9 36 72 Oss (CO) 16
Square pyramid 5 45 8 37 74 Fes (CO), 3 C
12C0 - Q6 CO Bicapped 6 54 12 42 84 056(CO)III
2a ;,2 e' tetrahedron
3e', e" Octahedron 6 54 11 43 86 Ru6 (CO),-C
Capped square 6 54 11 43 86 Os6 (CO;I, Q H ,
Fig. 2.42. Orbital interaction diagrams for M3 (CO)72 and [Pt3 (CO)5 ] 2- . Reproduced with per- pyramid
Triagonal prism 6 54 9 45 90 [Rb 6(CO) 15 C] 3-
mission from Lauher JW (1978) J . Am . Chem. Soc . 100 :5305
Capped octahedron 7 63 14 49 98 [Rh7(CO)16]' -
Square antiprism 8 72 15 57 114 [Co 5 (CO) 15 C] 2
Cube 8 72 12 60 120 Ni e (PPh)6(CO)e
Truncate hexagonal 13 117 32 85 170 [Rhl3(CO)24H3 ] 2-
Although MO-calculations do not specifically locate the metal-metal bonds, bipyramide
they always show the presence of three high-lying antibonding orbitals that
indirectly indicate the existence of the former. Reference
Theoretical calculations for other clusters with different nuclearities and Lauher JW (1978) J . Am . Chem . Soc. 100 :5305
geometries lead to qualitative similar results . Results obtained for some of most
common cluster geometries are summarized in Table 2 .20.
The application of this treatment appears to be successful in many cases,
Table 2.21 . Effect of unpaired electrons on internuclear distances in tricobalt clusters
often explaining the differences between different geometries, for instance be-
tween tetranuclear species. Tetrahedral, square-planar, or butterfly metal atom Compounds Interatomic distances (A)"
arrays may be differentiated by considering the corresponding molecular orbital
M-M A(M-M)6 M-X AIM X)'
diagrams and the number of electrons in the system . However the benefits of
such calculations do not go farther than those obtained from the analogy with FeCo 2(CO)9 S 2.544 0 .083 2.159 0 .020

f
boranes discussed above . Co3 (CO)9S 2.637 2.139
FeCo 2(CO) 9 Se 2.577 0 .039 2.285 0 .003
Theoretical descriptions may be to some extent verified experimentally . For Co3 (CO)9 Se 2.616 2.282
instance, the valence-band photoelectron spectrum of the compound [Fe(CO)7t-
Cp] 4 shows that, in agreement with the calculations discussed above, the Average values .
" Differences between interatomic distances d(M-M) and d(M-X) in the compounds FeCo 2(CO)9 X
highest occupied valence orbitals are actually metallic orbitals of the Fe, core . and Co3 (CO)9 X when X is S and Se respectively .
Mossbauer experiments of the same compound and of its oxidation product
[Fe(CO)7r-Cp]4 indicate that the unpaired electron interacts with the iron Reference
moiety. This feature is consistent with the theoretical model which establishes Strouse CE, Dahl LF (1971) J . Am . Chem . Soc. 93 :6032
the unpaired electron would occupy a delocalized MO with marked metal
character.
Electron Spin Resonance analyses of the 49-valence electron paramagnetic Table 2.21 on going from the diamagnetic species FeCo 2 (CO)9 X with 48 valence
trinuclear compounds, CO 3 (CO) 9S and Co 3 (CO) 9 Se, indicate that the unpaired electrons to the paramagnetic one Co 3 (CO) g X with 49, a significative increase in
electron in these compounds occupy a non degenerating antibonding orbital the average metal-metal distances is observed . This feature agrees with the
with a symmetry a 2 . The influence of this unpaired electron in an antibonding predicted antibonding nature of the unpaired electron . The metallic character-
orbital on the structural properties of the compounds is notable . As observed in istics of this last electron are also apparent in such experiments, since the


120 2 Transi
ion Me
al Clus
er Chemis
ry 2,4 Syn
hesis of Clus
er Compounds 121

enlargemen
effec
is observed only in
he me
al clus
er-no
in
he me
al-
ligands nor in
he me
al-chalcogen in
era
omic dis
ances .
2.4 Syn
hesis of Clus
er Compounds
Clus
er forma
ion is in general an agglomera
ion process in which labile in
er-
media
e species undergo condensa
ion reac
ions for giving produc
s wi
h higher
nucleari
ies . The ar
of syn
hesizing clus
ers is rela
ed
herefore
o finding proper
reagen
s and reac
ion condi
ions for genera
ing and condensing such kinds of
in
ermedia
es .
In ini
ial s
udies on
ransi
ion me
al clus
er chemis
ry syn
he
ic work was
frequen
ly based on chance discoveries . However
he explosive developmen
of

his branch of chemis
ry in
he las
fif
een years has also produced an accelera
ed
evolu
ion of clus
er syn
he
ical me
hods . On going from casual syn
hesis
o

ailored clus
er syn
hesis,
he sys
ema
ic prepara
ion of a grea
varie
y of homo
and he
eronuclear clus
er compounds is already possible .
Fundamen
al considera
ion of
he
ype of condensa
ion reac
ions involved
in clus
er forma
ion shows
ha

he me
hods mos
frequen
ly used for me
al
2 . The disrup
ion of one or more bonds
o produce unsa
ura
ed species .
Frequen
ly bo
h processes may be carried ou
simul
aneously in
he same

rial . In o
her cases, however,
he precursors in a low oxida
ion s
a
e are
prepared firs
and
hen
he condensa
ion reac
ion is induced by
hermal,
pho
ochemical, or chemical genera
ion of unsa
ura
e species .
Impor
an
pioneer work in
he syn
hesis of polynuclear me
al carbonyls was
made by reduc
ion of simple me
al sal
s in
he presence of carbon monoxide or
similar ligands . The bes
resul
s are ob
ained in general for
he mos
s
able
clus
ers such as
riru
henium,
riosmium,
e
rarhodium, and
e
rairidium
dodecacarbonyls. Thus, he
erogeneous pyrolysis reac
ions of me
al halides wi
h
carbon monoxide in
he presence of halide accep
ors such as Cu or Zn under
rela
ive dras
ic condi
ions of
empera
ure and pressure can be used for prepar-
ing
hese
ypes of
hree and
e
ranuclear carbonyl clus
ers :
4IrC1 4 + 12CO + 8Cu --=~Ir
1 4(CO) 12 + 8CuC1 2
350 aim
50+ sa -
4RhC13 + 12CO + 12Cu Rh4(CO) 12 + 12CuCI
200 aim

clus
er syn
hesis may be classified in
he following
hree groups :

Homogenous solu
ion reac
ions of
en offer
he possibili
y of carrying ou

1 . Condensa
ion reac
ions induced by
he presence of coordina
ely unsa
ura
ed
hese syn
hesis under considerably milder condi
ions :
species,
2 . Condensa
ion under reduc
ive condi
ions, n
Cou

3 . Condensa
ion reac
ions be
ween coordina
ely sa
ura
ed species wi
h differen
~` >Ir4(CO} 12 +. 16HC1 + 8C0 2
4IrCl4 + 2000 + 8H 2O
200 a
m
oxida
ion s
a
es, and
4 . Condensa
ion reac
ions induced by
he presence of special ligands . MeOH
6RuC1 3 + 33C0 + 9H 2O)2Ru 3(CO) 12 + 18HC1 + 9C02
5 10 a
m

2.4.1 Condensa
ion Reac
ions Induced by Coordina
ely Unsa
ura
ed Species The forma
ion of me
al carbonyl clus
ers by reduc
ion of
he me
al halides
appears
o occur via
he forma
ion of halo-carbonyl compounds as in
ermedia
e
For inducing
he forma
ion of me
al-me
al bonds, i
is, in general, necessary for species . Thus,
he reduc
ion of halide deriva
ives is of
en a good al
erna
ive for

he me
al a
oms
o exis
in a ra
her low oxida
ion s
a
e . Especially sui
able for
he forma
ion of clus
ers:

he syn
hesis of me
al clus
ers are
herefore elec
ron-deficien
fragmen
s in which

he me
al a
oms have
he same oxida
ion s
a
e
han
ha

hey will have in
he 0
9 *C,
2RhCl 3 (H20),, + 6CO Rh2(CO) 4C12 + 20001 2 + 2x "2 0
clus
er. These fragmen
s are normally very uns
able and labile species . Elec
ron
deficiency induces a coordina
ive unsa
ura
ion
ha
in absence of s
rong donor
j : 90%
species will
end
o form me
al-me
al bonds . 2Rh2(CO) 4C1 2 + 6C0 + 4NaHCO 3
Reduc
ion of Sal
s of Me
als in Normal Oxida
ion S
a
es. In many cases
he 25 *C
Rh4(CO) 12 + 6CO2 + 4NaCl + 2H 20
forma
ion of reac
ive fragmen
s can be achieved direc
ly from sal
s of
he me
als hexane (H,O)
in
heir normal oxida
ion s
a
es . In
hese processes
he following
wo s
eps q : 80-85%
should be dis
inguished: "C, 4 a
H )
41r(CO)2(CI)L + 4CO + 2Zn lr4(CO)
2 + 2ZnC1 2 + 4L
1 . A reduc
ion process
o ob
ain
he me
al in adequa
ely low oxida
ion s
a
e, 90' 2 a
m
and r
: 80-85


122 2 Transition Metal Cluster Chemistry 2 .4 Synthesis of Cluster Compounds 123

Reduction of halides has also been applied recently in the synthesis of giant Table 2.22. Selected examples of metal cluster preparations via photolitic and thermolitic methods
clusters : Reagents, conditions, and yield Ref.
Compound
B2H6
PhPAuC1
3 >Auss(PPh,}12 Cl 6
Benzene, 50-60°C [Re7C{CO)2,], - [Re(CO)4H]- ; n-tetradecane, A; 70% 1
Fe 3(CO), ; n-heptane, by
Fe(CO)5 2,3
[Fe5 N(CO) 14 [Fe2 (CO),] z + Fe(CO) s + NOBF4 ; 4
p-To1,PAuCI +(p-Tol 3 P) 4A $4Cia B
Na H, (P - Tol_ ) 12
1? Au
1s A
gzoCl to diglima, A; 66%
EtOH 2, 3, 5
Ru 3 (CO) 12 Ru(CO) 5 ; n-heptane, 30'C; h ; 100%
Ru6 C(CO) 17 Ru3 (CO) 12 + CH 2 Cl 2 ; A; 70% 6
Thermal Activation . Although the synthesis of carbonyl metal clusters directly Os 3(CO) 1Z Os(CO), ; n-heptane, 30'C; sunlight 2, 3
from high oxidation state derivatives was historically of great importance, it is Os 5(CO)„ Os 6 (CO} S8 + CO(90 atm) ; heptane, A; 80% 7
an intrinsically inefficient method because, as it will be seen in the next section, Os6(CO) 18 Os3 (CO} 1 2 ; vacuum pyrolysis ; 80% 8
Osb (CO),sH2S2 Os3 (CO) 10 H(SCH 2 C,,H5); by; N 2 . hexane; 8% 9
carbonyl metal clusters, in general, undergo degradation reactions in the pres- 10
0s 6(CO) 16(CPh) 2 Osb (CO) 1a + PhCCPh; by
ence of carbon monoxide . The method is therefore applicable only for the Os3 (CO), 12 hv; ( O) 10
34% 11
Os,Os7(CO)(CO)1,9S4
synthesis of thermodynamic and kinetic stable metal clusters . In the case of 9S Os,,(C0j 12 SSC0j + Os3(CO) (MeCN)2 ; 12
unstable compounds, for instance the carbonyl clusters of the elements of the octane, A; 23%
first transition metal series, obtaining cluster products is possible only by [Os,(CO)22H]- Os6(CO), O ; BuOH, A; 30% 13
[Os 1O C(CO)24] 2- Os3 (CO) 1 ,(C S H5 N); vacuum pyrolysis ; 65% 14
starting from metal carbonyls : 15
[Cob (CO) 1 S] 2 Co 3 (CO)s + (i)EtOH ; (ii), vacuum;
petroleum ether (iii) + H2O, K Br, 3(
2Co 2(CO)8 Co4(CO)1 2 + 4CO [Co6 C(CO), s ]2- [Co(CO)4] - + (i) Co(CO) y CCI; diisopropylether, 16
60-90 °C
A; (ii) KBr ; 70-80%
90% [Co6 C(CO) 15 ] 2 ; diglyme, A ; 40-50% 17
[Co13(C)2(CO)2a ]''-
Rh6 (CO) J6 RhC1 3 3HO + CO(40atm); MeOH; A; 80-90% 18
Binary metal-carbonyl complexes are known for most transition metals and
[Rh9 p(Co)21)2 Rh(CO) 1 2(acac) + CO, H 2 (400 atm) ; 80% 19
they are, in general, the more appropriate starting material in pyrolitic and [Rh, O P(CO) 22 ] 2- Rh(CO) 2 (acac) + CO, H 2 (400 atm) + Cs- 20
photolytic synthetical methods . [PhCOO] + Cs[BF4 ] + PPh 3; diglyme ; A; 98%
Pyrolyses of metal carbonyls are carried out either in inert solvents or, to [Rh 1Q As(CO)22 ] 2- Rb(CO) 2 (acac) + CO, H 2 (400 atm) + Cs- 21
facilitate the elimination of CO, in the solid state under vacuum . [PhCOO] + AsPh 3 ; diglyme, A ; 98%
[Rh13(CO)24H2] 3- Rh(CO) 2 (acac) + CO, H 2 (12 atm) +Cs[PhCOO]/ 22
Although thermal induced elimination of ligands is a very convenient (CH 2 OH)2 ; tetraglyme, A ; 91%
method to perform in the laboratory, it is very difficult to control the extent of Rh(C0 2 (acac} + CO, H 2 (200 atm) + Cs[PhCOO]/ 23
[Rh14(CO)23] 4 '
the elimination . Such reactions are therefore rarely specific leading to the (CH2OH)2 + N-methylmorpholine ;
formation of a variety of products whose distribution normally depends on their tetraglyme, 4 60%
relative stabilities. Reaction conditions are rather critical, hence for obtaining [Rh,,(CO) 27 ]' Rh(CO)2 (acac) + CO, H 2 (19 atm) + Cs[PhCOO]/ 24
good yields of a given product they must be carefully selected: (CH 2 OH)2 + N-methylmorpholine;
tetraglyme ; A ; 87%
50 'C 63 100 - C 120°C [Rh,7(S)2(CO)32]3 Rh(CO) 2 (acac) + CO, H 2 (300 atm) + Cs[PhCOO] 25
C02(CO)8 ~Coa (CO) 12 )Cofi(CO) 16 ' dec. + H2 O + H 2 S or SO2 ; tetraglyme, A; 73%
Ni 4 (CNBu'), Ni(CNBu1)4 + Ni(COD) 26
Pt 3 (CNBu') 6 Pt(COD)2 + 6CNBu' 27
In the case of relatively unstable compounds frequently all ligands arc lost 28
[Ptt,(CO)22] 4 ' [Pt 9 (CO) 1B ] 2- ; MeCN, A; 50%
and bulk metal is obtained : CrOs(CO),(PMe 3 k C,F 6, bv; 31 % 29
CrOs2(CO)11(PMc3)2
WOs3(CO)12(PMe 2 Ph)(S) 2 Os3 (CO)9 S 2 + W(CO) 3 (PMe2 Ph) + hv ; 27% 30
Ni(CO)4 c_). Ni ° W 2 0s3 (CO), 4 (PMe2 Ph) 2 (S) 2
[W2Ni3(CO),6] 2 [W 2 (CO)1O 1 2 + Ni(CO)4 ; THF, A; 68% 31
Fe2Pt(CO)aPR3)2 Fe 2 (CO)2 + Pt(PR 3 )a 32
130 170'C 33
Re2(CO)1o Reo [Fe3 Pt3 (CO) 15 ] 2 [Pt3(CO)61 2 + Fe(CO), ; MeCN, A; 70%
Ru4 Au2 C(CO), 2(PMe 2 Ph) 2 Ru s AuC(CO)14(PMe2Ph)2 + CO (8o atm) ; 34
70'C
toluene, A ; 80%
3Fe 2(CO) 9 3Fe(CO)s + Fe~(CO), 2-+Fe° [Os3 C.:o(CO) 13 1 - [CO(CO)4] - + Os3(CO)12 ; by 35


124 2 Transition Metal Cluster Chemistry 2 .4 Synthesis of Cluster Compounds 125

Table 2.22. (continued) Table 2 .22. (continued)

Compound Reagents conditions and yield Ref, 35 Burkhardt E . Gcoffsoy GL (1980)1. Organomet . Chem . 198 :179
36 Burgess K, Johnson BFG, Kaner DA, Lewis J, Raithby PR, Mustaffa SNAB (1983) J . Chem .
Os 3 Au2{CO) le 1PEt z Ja [Os 3 (CO) 1 ,H] - + Au(PEt3 )CI + TIPF6 ; 36 Soc., Chem. Commun ., 455
CHC1 3 , A; 80% 37 Chini P, Cavalieri A, Martinengo S (1972) Coord . Chem . Rev . 8 : 3
[Co4 N' 2 (CO) 14 ] 2- NiCl 2 + [Co(EtOH),] [CO(CO)412 + (i) vacuum . 37 38 Martinengo S, Ciani G, Sironi A (1984) J. Chem . Soc., Chem . Commun., 1577
(ii) KBr; H 2 O; 60% 39 Vidal IL, Troup JM (1981) J . Organomet . Chem . 213 :351
[Rh 6 IrN(CO)15 ) 2 [Rh6N(CO)15] 2 + [Ir(CO) 4 ] ; THF, 38
A ; 79-80%
[Rh 12 Sb(CO)2 -] 3- Rh(CO)2 (acac) + CO, H 2 (400 atm) + Cs[PhCOO] 39 In the synthesis of high nuclearity carbonyl clusters, small clusters are often
+ SbPh 3 ; tetraglyme; A; 66% used as starting materials :
210 `c
References Os3(CO) 12 )Os 6(CO) 15 + Os 5(CO) 16 + Os 7(CO) 21 + Os s (CO) 25
1 Ciani G, D'Alfonso G, Freni M, Romiti P, Sironi A (1982) J. Chem. Soc., Chem. Commun ., 339 80%
2 King RB (1965) Organoment . Synth. 1 :93 _
3 Moss JR, Graham AG (1977) J . Chem. Soc ., Dalton Trans., 95 Os3(CO) 11 (C5H 5 N)-[OstoC(CO)24] Z- + [Os5(CO)t 5H]
4 Tachikawa M, Stein J, Muetterties EL, Teller RG, Beno, MA, Gebert E, Williams JM (1980) 65%
J. Am . Chem. Soc. 102 :6648
5 Calderazzo F, L'Plattenier F (1967) Inorg . Chem. 6 :1220 + Os 5C(CO)14H(NC 5H4)
6 Johnson BFG, Lewis J, Sankey SW, Wong K, McPartlin M, Nelson WJH (1980) J . Organomet.
Chem . 191 :0
7 Farrar DH, Johnson BFG, Lewis J, Raithby PR, Rosales MJ (1982) J . Chem . Soc., Dalton Photochemical Activation . Coordinative unsaturated fragments may also be
Trans., 2501 produced by photolytic reactions . In presence of UV-irradiation metal carbonyl
8 Eady CR, Johnson BEG, Lewis J (1975) J . Chem. Soc., Dalton Trans., 2606
9 Adams RD, Horvath IT, Mathur P, Segmaller BE (1983) Organometallics 2 :996 compounds lose sequentially CO-ligands . Electron-deficient, solvent coor-
10 Fernandez JM, Johnson BFG, Lewis J, Raithby PR, (1978) Acta Crystallogr . Sect. B 34 :3086 dinated species produced in this way may combine with inactivated metal
11 Adams RD, Horvath IT (1984) J. Am . Chem . Soc . 106 :1869 complexes via the formation of donor-acceptor metal-metal bonds . Iron, ruthe-
12 Adams RD, Foust DF, Mathur P (1983) Organometallics 2 :990
13 Johnson BFG, Lewis J, Nelson WJH, Vargas MD, Braga D, Henrick K, McPartlin M, (1984)
nium, and osmium trinuclear carbonyl clusters may be prepared by this way :
J. Chem . Soc ., Dalton Trans, 2151
14 Jackson PF, Johnson BFG, Lewis J, Nelson WJH, McPartlin M (1982) J . Chem . Soc., Dalton M 3 (CO) 12 + 3CO
3M(CO)5-M3(CO)12 M = Fe, Ru, Os
Trans ., 2099
15 Chini P (1967) .1 . Chem . Soc., Chem . Commun ., 29
16 Martinengo S, Strumolo D, Chini P, Albano VG, Braga D (1985) 3 . Chem . Soc., Dalton Trans ., Thermolytic reactions are in general unfavorable for the synthesis of hetero-
35 nuclear compounds due to the lack of specificity of the method . Photolytic
17 Albano VG, Braga D . Chini P, Ciani G, Martinengo S (1982) J . Chem . Soc., Dalton "Tans ., 645 procedures require instead milder conditions and they can sometimes even used
18 Chaston SHH, Stone FGA (1969) J . Chem . Soc. A, 500
19 MacLaughlin SA, Taylor NJ, Carty AJ (1983) Organometallics 2 :1194 for synthesizing some heteronuclear monoanions :
20 Vidal IL, Walker WE, Schoening RC (1981) Inorg . Chem . 20 :238 _ by _
21 Vidal JL (1981) Inorg . Chem . 20 :243 [Co(CO)4] + Fe(CO) s->[FeCo(CO)s + CO
22 Vidal JL, Schoening RC (1981) J . Organomet . Chem . 218 :217
23 Vidal JL, Schoening RC (1981) Inorg . Chem. 20 :265
24 Vidal IL, Schoening RC (1982) Inorg . Chem. 21t :438 Os3(CO) 12 +[Co(CO)4 ] -[O8 3Co(CO) 1 2] - + 4CO
25 Vidal JL, Fiato RA, Cosby LA, Pruett RL (1978) Inorg, Chem . 17 :2574
26 Thomas MG, Pretzer WR, Beier BF, Hirsekorn FJ, Muetterties EL (1977) J . Am . Chem. Soc. Selected examples of preparations of metal clusters via thermolytic and
99 :743
27 Green M, Howard JAK, Murray M, Spencer JL . Stone FGA (1977) J . Chem. Soc., Dalton Trans., photolytic procedures are described in Table 2 .22.
1509 High-valence halide clusters of transition metals -in which the metal also
28 Washecheck DM, Wucherer EJ, Dahl LF, Ceriotti A, Longonl G, Manasscro M, Sansoni M, has an oxidation state lower than in normal salts-are normally prepared by
Chini P (1979) J. Am. Chem . Soc. 101 :6110
29 Davis HB, Einstein FWB, Johnston VJ, Pomeroy RK (1988) J . Am. Chem . Soc . 110 :4451 pyrolitic reduction of the mononuclear halide :
30 Adams RD, Horvath IT, Mathur P (1984) J . Am. Chem . Soc. 106 :6296
31 Ruff JK, White RP, Dahl LF (1971) J . Am . Chem . Soc. 93 :2159 3ReC1 5->Re 3 C1 9 + 3CI 2
32 Bruce MI, Shaw G, Stone FGA {1972) J. Chem . Soc., Dalton Trans ., 1082
33 Longoni G. Manasscro M, Sansoni M (1980) J . Am . Chem . Soc. 102 :7973 18TaX 5 + l6Al->3Ta 6X 14 + 16A1X,; X = Cl, Br, I
34 Cowie AG, Johnson BFG, Lewis J Raithby, PR (1984) 1 . Chem. Soc.,em,
Ch Commun .,Cl 1790
MoC1 5 + Mo->MoC1 3->Mo6, z


126 2 Transition Metal Cluster Chemistry 2 .4 Synthesis of Cluster Compounds 127

2A.2 Condensation Between Coordinately Saturated Species 3 3

M(CO) L
IFe5 MC( CO ) 17 12-
with Different Oxidation States M =Cr, Lc C5H5N ; M : M0, LzTHF . M, W . L=MeCN

Redox condensation of an anionic mono or polynuclear carbonyl species with Ni(COD) 2 -IFe5NiC(C0)t4(000)) 2
a neutral, cationic, or anionic fragment provides a valuable method for the
synthesis of carbonyl metal clusters . Pd2(C3H5)2CL2
.- Fe 5 PdC(CO) 16
Among the characteristics of this method are the mild reaction conditions
that avoid the degradation of the products and permit the formation of high-
nuclearity products . The facility with which such kinds of condensations occur is
tFeSC(CO)141
2
2 Ife 5 RhC(CO) 16 1`
Rh (C0) C1

probably due to the redox character of these reactions .

2
M (COD) CL 2 2 1
Reaction of metallates with neutral metal complexes . The reaction of cluster -IFeMC(C0) 4(C00)) ; M=Rh,tr
carbonyl metallates with neutral carbonyl compounds has proved to be very
useful in the preparation of homy and heteronuclear derivatives : F@2(CO)9 •- IFeSC(CO)t61 2 -
[Rh(CO)4] - + Rh4(C0) 12 -'[Rh 5(CO) ] 15 + CO
5
[Fe 3(CO) 11 ] 2- + Fe(CO) ->[Fe4 (CO)13] 2 + 3CO Fig. 2.43 . Reactions of [Fe2 (CO) 14 ] 2- with neutral species containing labile ligands (COD = 1, 2-
cyclo octadiene) [Tachikawa M, Geerts RL, Mueatterties EL (1981) J . Organoment . Chem . 213 : 11 ]

[Ru 3(CO) 11 ] Z + Ru3(CO) 12 ->[Ru6 (CO) 18 ] Z + 5CO

[Rh 6 (CO) 15 (N)] 4
+ M(CO) --'[Rh6 M(N)(CO) 15 ] 2 + 4CO
M=Cr, W 2 [Ru6C(CO) 16 12 + TI IN03 ) 3
McOH~~ '~~~
\K&

[Fe 3(CO)9(000)] 2- + Rh(CO) 2 (py)Cl->[RhFe 3(CO) 12 (C)] 2- [{Ru6C(C0116}2 TI] _

As can be seen, the chemical equations indicate that these reactions could
often be considered as carbon monoxide displacement reactions . The condensa-
14
tions involving the square-based pyramidal dianion [Fe 5C(CO) ] 2- and some 2[RuCO 3(CO) 12 1 +HgBr 2
neutral species with labile ligands shown in the scheme in Fig . 2.43 may be {RuCo3(CO)g 2119
cataloged into the same type of reactions . The same is valid in the desplacement
of the chlorine atom in the chloromethyl derivative Co 3 (CO) 9 CCl by mononu-
clear and cluster carbonyl metallates according to the following equations .
kh
Co 3 (CO) 9CC1 + 3 [Co(CO)4 ] --.[C0 6C(CO) 15] 2 + 6CO + Cl 3
3[Os (CO) 1 H] -+ HgBr 2 IN
_C1
1 .5[N16(CO)12]2 - [C03 Nig C(CO) 2() ] 3 + 7CO
C03(CO) 9CCl + __+
1•
Reaction of metallates with cationicc complexes. The synthesis of one of the
largest metal carbonyl cluster structurally characterized up to date . Os 9 Hg 3 (CO) 33
[Ni38 Pt 6(CO)48 H 2 ] 4- , has been obtained from the condensation reaction of the
Fig . 2.44. Reactions of metallates with TI and Hg salts [Vargas MD, Nichol) 3N (1986) Adv . Inorg.
metallate [Ni6(CO) 12 ] 2 with the platinum(II) salt PtC12 . Chem . Radiochem . 3a :123]
Coupling reactions of some metallates with salts of TI, Hg, or Au often
originate condensation products in which, as can be observed in the schemes in
Fig. 2.44, the basic cluster geometry is preserved . As observed in Fig . 2 .45, which
describes the condensation of [Rh6C(CO) 15 ] 2- with Ag(I), sometimes the with metallates. Condensation reactions of [Ru 4(CO) 12 H 2 ] 2- with cations
degree of condensation may be modulated by the reagents ratio . [M(PR 3 )] + described in the scheme in Fig . 2 .46 exemplifies this type of reaction .
Cationic fragments generated from complex salts of the metals copper, silver These complexes with weak coordinating contraions (PF6 CIO` etc .) react
or gold appear to be a powerful method for promoting condensation reactions readily in solution. In the case of halides, however, the presence of silver or


128 2 Transition Metal Cluster Chemistry 2 .4 Synthesis of Cluster Compounds 129

Charge 2- 3- 4- n- 2- 1- 0 Table 2.23. Cluster synthesis by condensation of metallates with neutral metallic species

Product Reagents Ref.

[MFe 3 (CO) 13 C] 2- : M = Cr, W Fe,(CO)6 (CCO)]2- + M(CO),(NCR) 3 I

[MFe 4(CU), s CJ 2 : M = Cr, W [! e4(CO) 12 C] 2 + M(CO)3L3 2
[M2Ni3(CO)16] 2 ; M = Cr, Mo, W [M 2 (CO), u ] 2 + 3Ni(('O)4 3
II
[MNi 4(CO) 17 ] x ; M = Cr . Mo, W M(CO) 6 + ( Ni6(CO) 12 ] 2 4
[MnFe2 (CO) 12 ] - [Mn(CO) 5 J + Fe3 (CO) 12 5
[MnNi2 (CO) 5 Cp2 ] - [Mn(CO) 5 ] - + Ni2 (CO) 2 Cp 2 6
[ReRu3 (CO) 16] - [Re(CO) 5 ] - + Ru3 (CO) 12 7
[Fe4(CO)13]2 Fe(CO) 5 + [Fe3(CO)I1] 2- 8
[M3 Co(CO), 3 ] ; M = Fe, Ru M 3 (CO) 12 + [Co(CO)4J 9
[Fe4 Co(CO) 14 C] [Fe4 (CO) 12 C]2 . . + Co 2 (CO) s 10
[Fe,Ni(CO) 14 (COD)C] - [Fes (CO), 4 C]2 + Ni(COD)2 2
[Fe4 M(CO) 16 ] 2- ; M = Pd, Pt 3[Fe,(CO),, 1 2 - + 2[MCI4]2- 11
[Fe3 Pt3 (CO), 5 ] 2 3Fe(CO) 5 + [Pt 3 (CO)6 ] 2 12
Compound (5) (6) (7) (e) (9) (10) (tt1 [Fe4 Rh(CO) 14C] [Fe4 (CO) 12 C] 2- + [ Rh(CO) 2 C]] 2 2
6
(Rh (CO) i5 C1 2- 1 2 3 1 3 2 S [RuCo 3 (CO) 12 ]' RuCo2(CO)11 + [Co(CO)4] 13
Ag+ 0 1 2 1 4 3 2' [Cos(CO)15CJ 2- 2[Co6(CO))5C] 2- +Co4(CO)12 14
[Rh7(CO)16] 3 [Rh6(CO)15] 1 + [Rh(CO)4] 15
Fig . 2.45. [Rh 6C(CO) 15 ] 2- ,•'Ag adducts at different clusters/silver molar ratios . Reproduced with [Rh7(CO)16I] 2 2[Rh6(CO)15] 2 + Rh2(CO)4I2 16
[Rh,2(CO)30]2 [Rh6(CO), ] 2 + Rh6(CO))6 17
permission from Heaton BT, Strona L, Martinengos, Strumulo D, Albano VG, Braga D (1983)
J . Chem. Soc. Dalton Trans . 2175 [Rh 6 Ni(CO) 16] 2 [Rh 6 (CO)„J 2 + Ni(CO)4 18

References
2[M(MeCN)1 + (M=Cu,Ag)
R u4 ( CO ) 12H2 (MMeCN)2 1 Hriljac JA, Holt EM, Shriver DF (1987) Inorg . Chem . 26 :2943
2 Tachikawa M, Geerts RL, Muetterties EL (1981) J . Organomet . Chem . 213 :11
3 Ruff JK, White Jr RP, Dahl LF (1971) J . Am . Chem. Soc . 93 :2159
2IM(PPh 3 )1+ (MoCu . Agl
Ru 4 (C0)12H2 (MPPh3)2 4 Hall TL, Ruff JK (1981) Inorg . Chem. 20 :4444
5 Anders U, Graham WAG (1966) J. Chem . Soc ., Chem . Commun ., 291
4
(Ru (C0) 12 14 6 Hsich ATT, Knight 1 (1971) J . Organomet. Chem . 26 :125
1(Ag(MeCN)1+ 1ICu(MeCN)1+ 7 Knight J, Mays MJ (1972) J . Chem . Soc ., Dalton Trans., 1022
Ru4(C0)12H2 (CuMeCN) I AgM .C N )
8 Hiehcr W, Shubert H (1965) Z . Anorg . Allg. Chem . 338 :37
9 Steinhardt PC. Gladfelter WL, Harley AD, Fox JR, Geoffrey GL (1980) Inorg. Chem . 19 :332
10 Hriljac JA, Swepston PN, Shriver DF (1985) Organometallics 4 :158
)1Ag(PPh3)l+ 1(Cu(PPh3)1 +
11 Longoni G, Manassero M, Sansoni M (1980) J . Am . Chem. Soc. 102 :3242
Ru4(C0)t2H2(CuPPh3)(A9PPh 3) 12 Longoni G, Manassero M, Sansoni M (1980) J . Am . Chem. Soc. 102 :7973
Fig. 2 .46. Condensation reactions of the anion [Ru 4 (CO) 12 H 2 ] 2 " with [MPR 3 ]* cations, Ref.: 13 Roland E, Bernhardt W, Vahrcnkamp H (1986) Chem. Ber. 119 :2566
Brown SSD, Salter ID, Smith BM (1985) J . Chem. Soc ., Chem . Commun ., 1439; Freeman MJ, Green 14 Chini P, Longoni G, Albano VG (1976) Adv . Organomet . Chem. 14 :285
M, Orpen AG, Salter ID, Stone FGA (1983) J . Chem . Soc., Chem. Commun. 1332 15 Martinengo S, Chini P (1972) Gazz . Chim . Ital . 102 :344
16 Martinengo S . Chini P, Giordano G, Ceriotti A, Albano VAG, Ciani Ci (1975) J . Organomet .
Chem . 88 :375
17 Albino VG, Ceriotti A, Chini P, Ciani G, Martinengo S, Anker M (1975) J . Chem. Soc ., Chem.
thallium salts is required . Further examples of condensation reactions of metal- Commun., 859
lates with neutral species are described in Table 2 .23 . 18 Fumagalli A. Longoni G, Chini P, Albinati A, Brunckner S (1980) J . Organomct . Chem . 202 :329

2.4 .3 Generation of Unsatured Species by Chemical Methods

Ligand elimination constitutes in some case an alternative way to produce The reaction with hydroxide ions appears to yield first hydromctal carbonyl
coordinativc unsaturated metal species . Trimethyl oxide and also the hydroxide anions,
ion can remove carbonyl ligands converting them to CO 2 . 0S 3(CO) 12 + OH -[HOs3(CO)11] + C02


If
130 2 Transition Metal Cluster Chemistry 2.4 Synthesis of Cluster Compounds 131

which under stronger conditions can condensate to produce large clusters . The possibility of governing the stoichiometry of the reactions by controlling
100 :C the quantity of added ligand, on the one hand, and the mild conditions under
Os3(CO) 1 z + OH- [H3 Osa( CO)~ z] - + jHOs~{CO), s] -
48 h which the cluster-forming reaction can be performed, on the other, are the two
45% 18% principal advantages offered by these methods .
+ other products
Reactions of carbonyl compounds with Me3NO appear to depend on the
2.4.5 Ligand-Assisted Condensation Reactions
ability of the medium to stabilize the intermediate products . In very poor
donating solvents, condensation does occur, but relatively drastic conditions are There are some ligands which have the property of bonding many metal atoms
needed ; however the specificity of the reactions is poor . simultaneously-holding them together and thus inducing the formation of
RO=C metal-metal bonds . Many of the more effective bridging ligands are derived from
71-CpRh(CO)2 + Me3NO ' 7z-Cp 2Rh2(CO) 3 + n-Cp3Rh3(CO)3
10-25% the heavier members of the main groups: GeR 2i SnR2, PR2, AsR2, SR. etc.. Also
30-60%
some small unstable fragments such as RN, RC, RP, 5, etc . can lead to the
+ 1l-Cp4Rh4(CO) 2 aggregation of metal atoms around themselves supporting thus metal-metal
5% bonds . Although these fragments are very reactive species that can not exist
Better results are achieved when these reactions are performed in weak separately, joined to metal polyhedra they form rather stable cluster com-
donating solvents such as acetonitrile which can stabilize the decarbonylated pounds.
intermediates: Although compounds with edge and face-bridging ligands may be formally
McCN considered as main group-transition metal mixed clusters (s . Chap. 3), in these
M(CO)x + nMe3NO--~M(CO).,_ n{MeCN)„ + nCO 2 + nNMe 3 section they will be referred to only as ligands .
The condensation processes involved in the formation of metal-metal bonds
These lightly stabilized complexes easily undergo substitution processes in assisted by the presence of main group bridging ligands (E) are often initiated by
which the weakly coordinated ligand is displaced by other uncharged a displacement reaction. In the case of two metal complexes L„ ME and L,,,M',
18-electron metal complexes . This kind of reaction will be referred to in the next an electron lone pair on the ligand E can displace a ligand in the second complex
section in discussing displacement reactions . forming a bridged binuclear species which by further ligand eliminations finally
leads to a new metal-metal bond .
2 .4.4 Displacement Reactions
E: E E
Very useful as synthetic methods in cluster chemistry are the displacement
reactions of weak coordinated ligands such as MeCN, THF, Py, alkenes and L n + M . Lm - L n M \ L m-1 L n _1 M-M' CM-1
others. Complexes containing these ligands may be prepared by thermal, photo-
chemical, or chemical methods.
The relatively high specificity of displacement mechanisms assisted by bridg-
n, ing ligands make such reactions useful for the synthesis of heteronuclear com-
Cr{CO}6 -~Cr(CO)3{NCMe) 3 + 3C0
Nf Mc pounds. The reaction scheme in Fig . 2 .47 shows an example in which by using
the bridging and donor capacity of the group AsR 2 a new heteronuclear metal-
'~-'NO
Os3(CO)12 Os3(CO) t 1(NCMe) metal bond is achieved . This corresponds to the reaction sequence used for
NCMe obtaining the first cluster with four different metal atoms .
These lightly stabilized complexes may be then substituted by donor metal The validity of the ligand displacement mechanisms in ligand-assisted cluster
complexes by the formation of metal-metal bonds : synthesis mentioned above as well as the capability of the sulfur ligand to bind
several atoms simultaneously may be appreciated in the synthesis scheme shown
Os3(CO) 1 t(NCMe)
11,o5iCO),
'HZOs4(CO)15 in Fig. 2 .48. The reaction proceeds in two steps . In the first one, M(CO) 5 groups
~; are assembled around the sulfur atom by displacement reactions on the light
lre,tco)„tc:»z stabilized M(CO) 5THF units . In the second step, metal-metal bonds are formed
Cr{CO}3 (NCMe) 3 >[FeSCr(CO)17(C)]2- by elimination of carbon monoxide . This last step is reversible . Since these


2.4 Synthesis of Cluster Compounds 133

132 2 Transition Metal Cluster Chemistry

As Os_ `Os -
5 /
Os - S
CpW(C0) 3 AsMe 2 Co ( " 0s ~
Co Fe~ o 05 4 (Colt 2(03-S)2+0s3O)10NCM2 CO s- S
CO / \
+ ~W Ma-Fe I s /~7
Fe Cc MoSCp(CO) B \ 0s
.-
/ As \Wl

0s-Fig Os7(C0)20('L4-S) 2
.2.47 . Formation of heleronuclear metal-metal bonds by condensation reactions assisted by
ligands u 2 -AsR2 [Richter F, Vahrenkamp (1979) Angew . Chem • Int. Ed. Eng] . 18 :531]

\I/ 1~
\RS\ Ru-
R
Ru
Ru(C015 RU(C0)5
(C0) SM -l z / f S
-Ru-$- Ru=
1 ~Ru S
b +Co O C \1 / C0
1SH - \ M(CO)5L \ /
M (CO) 6 Ru-
2 M(CO) 5 L t `' Ru m ~R \
3 NaH (CO)5M/ I1

M(C0) 5 12 M(C01 4 -1 2 l 1RI Ru,

- Co Ru -Ru- um
_ -co oc~ l

+co +CO / -
(OC) 5 M S M(CO)5 MM { C 01 5
(OC) 4 l1/S\ - Ro`R S Rum u
~Ru Rug

Ru-Ru_ Ru
/l\ /I it\
M(CO) 3 -12 l0) 3 1

Fig . 249 . Synthesis of large clusters by bridge assisted additions [(a) Adams RD (1985) Polyhedron
c 0c 4 :2003; (b) Adams RD, Babin JE, Tasi M (1987) Inorg . Chem . 26 :2807]
~/i~ +ca ~ co

o V/ s`J o " - CO r `~s~ J

(CO) 4M M(CO)4 (OC) ~ / M(C0) 3
M C
0
Carbido and nitrido ligands also have been utilized as a multidentate ligand
Fig . 2.48 . Metal aggregation around a sulfur site [Darensbourg D3, Zalewski D1, Sanchez KM,
Delordt T (1989) lnorg . Chem . 27 :821] system capable of aggregating metal atoms and thus of inducing the formation
of clusters . Good precursors to bridged carbido and nitrido ligands are
ketenylidene (z-CCO) and cyanate (-NCO) ligands .
clusters are synthesized step by step, it is possible to incorporate different metal The reaction scheme in Fig . 2 .50 shows an example of how a ketenylidene
atoms into the same discrete metal cluster . The three metals and the sulfur atoms metal complex can be used as precursor for a bridged carbido ligand that can be
form a tetrahedral mixed cluster . This trinuclear metal cluster can react with subsequently used for preparing a variety of new heteronuclear complexes .
a fourth pentacarbonyl fragment to give pentanuclear derivatives . However the Similarly, the cyanate ligand in the cluster Ru,(CO)13(NCO) may be de
last metal ligand attaches itself to the sulfur but does not form new additional bonylated upon heating to yield nitrido clusters which can be enlarged by
metal-metal bonds to the other metal centers of the cluster . a sequence of redox condensation reactions .
This type of bridge-assisted addition, which is in general feasible for clusters ~s c Rutcrn,
possesing ligands with electron lone pairs, can sometimes be used for obtaining Ru4(CO)r3(p2-NCO) Ru4(CO)tz(p4-N)
c 4 co
high nuclearity clusters, as shown in the instances described in Fig . 2 .49 . In these
cases, cluster enlargement occurs by self-condensation under appropriate condi- Ru(co), N
-.Ru5(CO)t4(N5-N) }CV Ru6(CO)t6 (p6")
tions, or by addition of lightly stabilized clusters .


134 2 Transition Metal Cluster Chemistry 2 .5 Cluster Reactivity 135

00 ,2 - The oxidative addition of hydride and halide derivatives of the 14 and 15

'/ main group elements to neutral polynuclear metal compounds can also be used

I
C` Fe for obtaining clusters with bridging ligands .
/Fe\ co
+ Mn(CO) 5(NCMe)+ _N-2
CM,
3 Fe(CO)5 + 2 PhPH 2 -Fe 3 (CO) 9 (u 3-PPh)2 + 6CO + 2H2
Few
/J\
3/2Co 2(CO) 8 + PhGeH 3-Co,(CO) 9 (p3 -GePh) + 3CO + 3/2H 2 .
Fig. 250 . Preparation of carbide clusters front kelenylidenc metal complexes [Hriljac JA, Swepson
PN, Shriver DF (19851 Organotnetallics 4 : 158] Heteronuclear metal clusters may also be produced by this method .

C 02(CO)8 + Fe(CO) 5 + PhSH+FeCo 2(CO) 9 (p3-S) + C 6H 6 + 4CO

FeCo(CO) 7 (p 2 -PHR) + Co(CO)3(C3 H 5 )-2FeCo 2 (CO) 9 (1t3 -PR)

Ligand displacement reactions leading to the aggregation of metal atoms
around a main group ligand and subsequently to the formation of metal-metal + C3H6
bonds can also be achieved by the reaction of metallates with halides of 14 or 15 Cr(CO) 5 (PH 2 R) + Fe 3 (CO) 12 -sCrFe 2 (CO) t 1 (p3 -PR) .
main group elements .
3[Co(CO) 4] + RCC1 3 -+Co 3(CO) 9 (ft3 -CR)
2 .5 Cluster Reactivity
3[Co(CO) 4] + AsCI 3 -pC0 3 (CO)9 (u3 -As)
The halide displacement from the already coordinated ligands can lead to Metal atoms with low oxidation states and high polarizability of both metal-
clusters in good yields . As illustrated by reaction schemes in Fig . 2.51 this is metal and metal-ligand bonds make metal clusters susceptible to a variety of
a good method for the synthesis of heterometal clusters . chemical reactions . Depending on the reagents and reaction conditions, metal
cluster species are able to undergo nucleophilic and electrophilic substitution
reactions . homo and heterolytic bond dissociations, and redox processes . How-
ever, the great majority of cluster reactions appears to be complex processes in
MQ 2 Me t
As As which is not always possible to recognize these fundamental processes . In

\1/
general the knowledge about reaction mechanisms of cluster reactions is still
a (CO) 5 CrAsMe 2 Cl + NoM \ by \ I/ \ lacking. Therefore, although important advances have been made in the elucida-
/l -Co / Cr M tion of particular cases, any classification of cluster reactions must be still
established more by their products than by mechanistic considerations .
M= CpMo(CO) 3 , CpW(C0) 3 . Mn(CO) 5 , Re(CO) 5 and Co (CO), By considering the oxidation states of metal atoms, reactions may be
roughly classified into two groups: Reactions involving changes in the oxidation
states of cluster metal atoms and the reactions in which metal oxidation states
I remain unchanged .
\P/ From the point of view of cluster reactivity, those reactions in which the
- Br P
/ \ + Mn(CO)5 cluster structure is either conserved or modified by structural and nuclearity
I C0
changes but retaining its cluster nature are more interesting . However reactions
b /Fe-Co\ ~Mn co-
leading to degradation and disruption of the clusters must be often considered .
oC - /
/I\ 2.5.1 Reactions With Changes in Cluster Oxidation State
Fig . 251 . Synthesis of heteromeial clusterS by displacement reactions on coordinated cluster ligand
[(a) Ehrl W, Vahrenkamp H (1973) Chem . Ber . 106 :2550; (b) Muller M, Vahrenkamp H (1983) Redox reactions are very frequent in the chemistry of transition metal com-
Chem . Ber. 16 :2322] plexes . d-orbitals are forming there many relatively low-lying occupied and


136 2 Transition Metal Cluster Chemistry 2 .5 Cluster Reactivity 137

unoccupied molecular orbitals which permit a variety of oxidation states . Table 2.24. Examples of redox processes in metal clusters
Among metal complexes, clusters arc specially appropriate for redox reactions .
Type of Reaction Comments Examples Ref .
As discussed in Sect . 2 .3, the formation of a metal network gives rise to many reaction
new electron energy levels which can participate as donor or acceptor centers in
electron exchange processes . In many cases metal clusters are indeed able to act Electron- [M-M)" ±ne - Oxidation and [Nh6 Br, 2 ] 2- -2c" 1
Transfer ~LM-M],"," •- reduction by -[Nb,Br,2]°-
as electron reservoirs. The best examples of the electron transfer versatility of chemical or n.426V (SCE)
cluster compounds are the iron-sulfur clusters, which because of their biological electrochemical
importance will be discussed separately in Chapter 5 . electron-transfer. [Os6 (CO), 5 ] 2- + l Z 2
Os6(CO), e
Because of the nature of metal clusters, assignation of oxidation numbers to
Proton (M-M]" + H' Oxidation by [Ru„(CO),B]2- + 2H'
individual metal atoms as it is usually made for mononuclear species does not H 2 Ru 6 (CO), B
Addition -~ [M-M-H]"t 1 proton addition
1+
make sense in the case of metal aggregates . Cluster polyatomic metal nucleus yielding metal
must be considered as a whole, so only average oxidation numbers or states can hydride cluster . [H1r4(CO)„]' +H' 4
- H 2 Ir 4 (CO)„
be assigned to individual atoms .
The oxidation state of a cluster may be formally defined by considering the Base- M-M + L Soft Lewis-base Os,(CO), 6 + P(OMe), 5
Induced -M : L addition induces Os5(CO)te[P(OMe)3J3
skeleton valence electron counting as established in Sect . 2 .3 . An alternative Degradation metal-metal bond
method could be the same counting but without considering the electrons being breakdown Os 5 (CO), 6 + CO 5
. Os 5 (CO) 19
-
involved in the valence shell of the ligands . Dividing these metal valence
electrons among the metal atoms involved in the cluster, an average number of Oxidative M-M + L : L' Simultaneous Os 3 (CO), 2 + X 2 6
Addition ML + ML' addition of the -~ X[Os(CO)4 ] 3 X
electrons per metal atom useful for comparisons between clusters independent fragments of a
of their nuclearities may be obtained . An increase in the number of electrons in covalent species Ru 3 (CO), 2 + HX 7
the metal skeleton implies, in general, a reduction of cluster species whereas - (p2-H)Ru3(CO),n(i 2 -X)
cluster oxidation will be associated with a diminution in electrons in the
polyatomic metal nucleus . Nonetheless, there is not a unique method which References
could be useful and consistent in every case . As it will be often seen in this I Espenson JH, McCarley RE (1966) J . Am. Chem . Soc. 88 :1063
Chapter, the evaluation of changes in oxidation states is in many instances more 2 Eady CR, Johnson BFG. Lewis J (1976) J . Chem. Soc ., Chem . Commun., 302
a criterion matter than a response to a predeterminated pattern . 3 Eady CR, Jackson PF, Johnson BFG, Lewis J, Malatesta MC . McPartlin M . Nelson WJH (1980)
Table 2 .24 illustrates schematically some ways by which changes in the L Chem . Soc ., Dalton Trans., 383
a
Farrar F P Rosal M m. 94 :99
oxidation state of cluster species may be achieved . The simplest one by which 45 F J, Raithhy
a DH, Johnson BFG, Lewis J, G tbby PR, Rosales MJ (1982)1 . Chem. Soc, Dalton Trans .,
a redox process can occur is the addition or substraction of electrons or protons 2501
6 Cook N, Smart L, Woodward P (1977) J . Chem . Soc., Dalton Trans., 1744
without producing big changes in cluster structure . 7 Tachikawa M . Shapley IR (1977) J . Organomct. Chem . 124 : C19
Degradation processes leading to a diminution in the number of metal-metal
bonds with concomitant formation of metal-ligand bonds imply in general
cluster oxidation . On the other hand, the conversion of metal-ligand bonds in Lion about the number and relative stability of the species formed on the
metal-metal bonds increasing thus the cluster nuclearity implies in general electrode . Moreover, sometimes kinetic and mechanistic features associated
a decrease in the oxidation state of involved metal atoms and thus a reduction of with the electron transfer processes may also he investigated by this method .
the cluster species as a whole . Coulommetric measurements and exhaustive electrolysis are also useful as
In the following description of cluster reactions involving changes in cluster complementary techniques for determining the number of electrons associated
oxidation states both electrochemical and chemical processes will be considered . to investigate redox processes as well as a method for obtaining products of
In order to systematize the chemical redox processes, they have been roughly electrochemical reactions at a preparative scale .
cataloged as reduction, oxidation, or additive oxidation reactions . The analysis of electrochemical reactions by cyclic voltammetry depends
fundamentally on the stability of their products under experimental conditions .
Electrochemical Processes . The simplest type of redox reaction in cluster them- In general species with half-life times of the order of seconds are needed for this
istry is the direct addition or removal of electrons at an electrode surface . Cyclic technique.
voltammetry has proved to be a very useful electrochemical technique for In Table 2 .25 some selected examples of electrochemical reactions of metal
studying this kind of rcdox process . It permits us primarily to obtain informa- clusters are described .


138 2 Transition Metal Cluster Chemistry 2 .5 Cluster Reactivity 139

Table 2.25. Selected examples of electrochemical electron-transfer processes in metal clusters One typical case exemplifying the ability of some cluster compounds to
Cluster Products Comments Ref. undergo redox processes is the cubane cluster [7t-CpFe(CO)] 4 whose cyclic
voltammogram is illustrated in Fig . 2.52. Observed waves corresponding to
[Ta 6C1 12 ] 4 + [TaC1 12 1 3+ Acid water solutions . Reversible, rapid I totally reversible, one-electron processes can be assigned according to following
[TaCl 12] 2 + electron-transfers at 0.25 and 0.59 V (SCE);
cluster remains intact . equations,
[CpFc(CO)] 4 [CpFe(CO)] ; Dichloromethane 0.1 M [NBu 4 ](PF6 ) 2
[CpFe(CO)] 4 PF,; quantitative oxidation ; product insoluble [7r-CpFc(CO)]4+--> [x-CpFe(CO)]4 [7r-CpFe(CO)] 4
1 .07 V 0 .32 V
in reaction mixture .
[CpFe(CO)J 4 PF 6 [CpFe(CO)]4 Acetonitrile, 0 .1 M [NBu 4]PF6 . 2
[CpFe(CO)] 4 Electrochemically reversible processes : [7r-CpFe(CO)]a
-1 .30 v
CCPFe(CO)]4` [Fe4]2+/[Fe4]', 1 .08 V; [Fe4]'/[Fe4],
0.32 V; [Fe4]/[Fe4]-, - 1 .30 V. Potentials are measured with a Saturated Calomel Electrode (SCE) as reference .
Monoanion [Fe4] not isolated because
of extreme air sensitivity . Dication Although all these species are stable in the time scale of this technique, their
detected only by cyclic voltammetry separation from the reaction mixture is not always possible . The anionic species
(200 my s'* '). [7t-CpFe(CO)]4 is stable in solution for a long time but its reactivity, specially
[CpFeS]4 [CpFeS]4 Acetonitrile, 0 .1 M Bu 4NPF6 . Four 3
[CpFeS] 4 PF 6 electrochemically reversible one-electron
toward dioxygen producing [n-CpFe(CO)] 4, prevents its being obtained as
[CpFeS]4(PF6)2 processes: [Fe4]3+/[Fe4]2+, 1 .41 V ; a solid salt. The dicationic species [rr-CpFe(CO)14 + is stable only in the time
[CpFeS14' [Fe4J 2+ /[Fe4] + , 0.88 V; [Fe4]'/[Fe4], scale of the measurements. It decomposes rapidly in acetonitrile leading to the
0.33 V; [Fe 4]/[Fe4 ] , - 0.33 V . Salts
of mono and dication arc isolated in
degradation products Fee and [rr-CpFe(CO) 2CH 3CN]4 . The monocation
60-70% yields . [7r-CpFe(CO)]4 is stable and can be obtained by both, chemical and electro-
(Cp) 3 Co 3S 2 [(Cp) 3 Co 3 S 2 ]' llenzonitrile, Pt-electrode; three 4 chemical oxidation of the neutral compound . Crystallographic characterization
[(Cp) 3 Co 3 S 2 ] 2 + one-electron electrochemically reversible of the cation indicates that its structure is similar to that of the neutral
[(Cp) 3 Co 3S 2 ] - processes: [Co3]2+/[Co]3+, 0.57 V; compound . The oxidation produces only a small distortion of the geometry
[Co3]'/ •o31, - 0.12 V ; [Co3]/[Co3] ,
[(
- 1 .13 V. Potentials referred to Ag/AgCI . Td of the Fe4-core and a small diminution in the average metal-metal distance
Co 3 (CO) 9 S [Co3 (CO)9S]+ Dichloroethane, one near-revcrsihle, 5 (0-036 A).
[Co3 (CO)9 S]2- one-electron oxidation at + 0 .04 V and The cyclic voltammograms of high-valence clusters [M 6X 12] 2 4 (M = Nb or
one irreversible two-electron reduction
at - 1 .1 V. Potentials referred to
Ta; X = Cl, Br) in aqueous acid solutions show two reversible waves which
Ferrocinium/Ferrocene (Fc+/Fc) couple . correspond to two consecutive one-electron transfers . Oxidized species retain
Monocation stable only in solution .
RCCo 3 (Cp) 3 CR' [RCCo3 (Cp) 3 CR'] - R, R' = Ph, Ph; Ph, H; Mc3 Si, H; 6
[RCCo3 (Cp) 3 CR']+ Me 3Si, I . Dichloromethane or acetone . Fe4* -+Feq
[RCCo3 (Cp) 3 CR'] 2 * One electrochemically irreversible
reduction and two oxidations, one -40
reversible and one irreversible near the Fe4 -Fe4
solvent limit: [Co 3 ] " ,/[Co3], ca . - 1 .5 V
[Co3]/[Co3] +, ca . 0.6 V; [Co 3 ] ' /[Co 31'
,,
1 .3 V (vs. Ag/AgCI) . For R = R'=lerrocene, -20
redox-series is extended to [RCCo 3 (Cp) 3 Fe4 _Fe;
CR'
-O
References
1 Cooke NE, Kuwana T, Espenson J (1971) Inorg . Chem . 10 :1081 -20
Fe ; +Fe:
2 Ferguson JA, Meyer TJ (1972) J . Am . Chem . Soc. 94 :3409
3 Ferguson JA, Meyer TJ (1971) J . Chem . Soc. Chem . Commun. . 623 Fig. 252 . Cyclic voltammogram of
4 Machach T, Vahrenkamp H (1981) Chem . Her. 114 :505 compound [a-CpFe(CO)]4. Re-
5 Honrath U, Vahrenkamp H (1984) Z . Naturforsch. B39 :555 -40 produced with permission from
;
;-F-
Fe
6 Colbran CBI Robinson BH , Simpson J (1984) Organornetallics 4 :1344 - fo.t' 'l
Ferguson JA, Meyer, TJ (1972) J .
1 l i I Am . Chem. Soc . 94 :3409
Further examples and references in Meyer TJ (1975) Progr . Inorg. Chem . 19 : 1 ; Zanello P (1988) 1.0 .5 o.0 • .s -1.o
Coord . Chem. Rev . 83 :199; Len+oine P (1988) Coord . Chem . Rev. 83 :169 Volts vs SSCE


2.5 Cluster Reactivity 141

140 2 Transition Metal Cluster Chemistry

their structures after the electron transfer so the equilibria between cations with
charges 2+ , 3+ and 4 + are possible .
~~
nss[M`'Jvt`] t +
a+ 3+
[M6X 2 [M,,X12]
-o .55V
Redox potentials (vs SCE) in the scheme above correspond to those of the
bromide derivatives .
Chemical Oxidation Reactions. Atmospheric oxygen, weak oxidants such as
iron(II) chloride, mercury(II) or copper(II) salts, and protonic acids are oxida-
tion agents frequently used for oxidizing metal clusters .
Many metal clusters are air-stable compounds . However those of the first
transition metal series are in general more sensitive to air . Thus, binary carbonyl
of ruthenium, rhodium, and iridium are rather air-stable species while those of
iron, Fe 3 (CO), _, and cobalt, C 0 4(CO)12 , rapidly decompose apparently via
iron,
formation of the carbonates .
Mild oxidant agents often permit oxidations with retention of the cluster
structures . One example of this kind of simple chemical electron-transfer reac-
tions are the oxidations of niobium and tantalum clusters [M 6 X 12 ] 2+ to the
species with charges 3 + and 4+ . The reaction with iron(III) chloride and
cerium(IV) salts leads directly to the cations [M 6 X 12 ] 4+
However, in spite of the formation of Co,(CO) 1 6 in the last reaction, the
diversity of products observed indicates a reaction mechanism much more
complex than a simple electron transfer .
As mentioned above carbonyl clusters are in general labile to restructura-
tion . This property is normally enhanced by electron transfer reactions which
indeed promote processes leading to new structures that agree better with
the electron counting. Molecular-orbital studies like those for the cluster
. In
[7z-C 5 H5FeS], illustrated in Fig . 2 .53 permit to understand such a behavior
metal clusters the HOMO and the LUMO are usually metal-metal bonding and
antibonding molecular orbitals respectively . Electron transfer to clusters often
results therefore in a weakening of metal-metal interactions favoring cluster
fragmentation or, at least, lowering the activation barriers to structural re-
arrangements via metal-metal bond rupture . In general, this tendency to under-
go polyhedron rearrangements increases with increasing cluster nuclearity .
TETRAMETALS SYMMETRY MO's LIGAND
SYMMETRY
ORBITAL
ORBITAL S
o,+e+t l +21 2

[M6 X1212-1" Feel, [M6X12 ]4+

a, • t2
or Cetly) 4p a t +e+t 1 +21 2

Meanwhile in the reactions with milder oxidation agents, e .g. Hg(II) or Cu(11)
salts or iodine, intermediate oxidation states of the clusters are obtained . 4s a,+ t Z

Bg(lI)
[M6Xtz ]2+ s[M 6 X 12 ] 3 + a+t l . t2
Ce(II) or h
The oxidation of carbonyl metal clusters is in general of greater complexity . 3 d 01$2e+ 2t 1.31 2 tj + t 2
Especially when strong bridging ligands are lacking, changes in electron count-
ing are often associated with structural rearrangements and, frequently, also at+ e • tz (C 5 H 5 )
et + tl+t2
with nuclearity changes . Another factor which also plays an important role in e 1 1•
the stabilization of the oxidation products is the reactivity of carbonyl clusters
a l +e+t,+21 2
with carbon monoxide . The presence of carbon monoxide in the reaction
mixture often induces subsequent reactions leading to rearrangements as well as e + 11,12
tC
3S)
to cluster degradation and recombination of the fragments . 02 5H 5 )
In some cases, the oxidation of carbonyl cluster species with mild oxidants ° ' `°+ t,+u2
can occur without changes in their nuclearitics .
H I PG, or H 2S0 + or ( al +t2 3s(S)
_ ('ultl or Ag(ll sa115 01

[Fe3PL3(CO)15]` [Fe3Pt3(CO)15] ' l a) + t 2
+ '2
oH - in McOH

fHgC%)' - or FeCl, Fig. 2_53. Molecular orbital scheme for [>t-CpFES], [Trinh-Toan, Tel) BK, Ferguson JA, Meyer
CCo6(CO)15] _ 'COI(CO)16 C 0 4(CO)IIz + Co t +
25 °, H2 () Ti, Dahl LF { 1997) J. Am . Chess. Soc . 99 :408]


142 2.5 Cluster Reactivity 143

2 Transition Metal Cluster Chemistry

In the chemical oxidation of the anion [Os,(CO),,]2- by iodine leading to

the neutral species the cluster nuclearity is retained . ,A Fig . 2 .54. Condensations reactions by oxida-
tion of [Rh 5C(CO), s ] :1 - by FeQll}salts [Al-
bano VG, Chini p . Martinengo S . Sansoni M,
Strumolo DJ (19741 J . Chem. Soc. . Chem.
[OS6(CO)1 8] 2- - [Os6(CO)18] ~>• Fe 3 ./ 0 ' Commun., 299]
d/ Rh 8 C(CO) i9

However, a reorganization of the metal polyhedron from an octahedral to 1 R h 6 C(CO) 15 1

2
a bicapped tetrahedral geometry is observed .
Iron(Ill) salts are often used as oxidant agents in carbonyl cluster chemistry .
However, depending on the nature of the metal cluster as well as on the reaction
conditions, different processes may occur .
The oxidation of [Co 6C(CO) 15 j 2- (with 90 valence electrons) by FeCI 3 MR

"VON
with the loss of one mole carbon monoxide is also accompanied by cluster
rearrangement from the original trigonal prismatic to an octahedral geometry . ~
[CoC(CO) 15 ] 2 + FeC1 3 - [CoC(CO) 14 ] - + FeC1 2 + C1 - + CO (Rh 1 5 (C) 2 (C0)28 1 -

The same oxidant FeC1 3 may in many instances cause cluster degradations
as occurs in the conversion of the octahedral species [Fe 5 MC(CO) 17 ] 2- or
[Fe 5 MC(CO) 16 ] 2 ` to the corresponding square-based pyramidal clusters .
nitric acid where, beside the formation of the rhenium(1 V) salt Cs(ReCI 6 ), cluster
ligand exchange of chloride to nitrate to an extent of ca . 17% is achieved .
[Fe s MC(CO) 17 ] 2- F-ec-T ' Fe 4 MC(CO) lr, M = Cr, MO, W
Cs(ReCI 6 )
CsNO,
Re 3Cl 9
[Fe 4 MC(CO) 16 ] 2- F`o~' .[Fe,MC(CO)14]- M = Rh HNO, . C
(CS 3 Re 3 Cl q )(NO3)3
U

In some cases, the oxidation may proceed with concomitant addition of Oxidation of metal clusters may also be performed by reaction with
carbon monoxide as occurs in the oxidation of [Os 5 (CO) 15] 2 - with FeCl 3 Bronsted-acids through straightforward addition of protons to metal backbone .
under CO-atmosphere . Thus, carbonyl clusters of ruthenium, osmium and iridium are stable in acids
l and may be protoned without decomposition . The 'H-NMR spectra of these
F :
-̀
carbonyls in concentrated sulfuric or trifluoroacetic acid indicate the formation
[OsS(CO)15]2- CO Os 5(CO) 16
of cationic metal hydrides ;
As illustrated in the scheme in Fig . 2 .54, condensation reactions in which the
nuclearity of the products increases may also be achieved by oxidation with an H 2SO4 M=Ru,Os
iron (III) salt . M 3 (CO)t2 $ W 1HM3(C0)121
90 06

Acids as Oxidant Agents . The reaction of metal clusters with oxidant acids such H2SO4 • {H 2 lr 4 (CO)BL4] 2+ L=Co,PR 3
as nitric or sulfuric acids often produces cluster breakdown leading to salts of lr4(CO)6L4 + 2W
or CF 3COOH
the metals in higher oxidation states .
25'C Affinity of cluster species to protons increases with increasing electron
Rh4(CO)12 + 4H2SO4 _~ 4[Rh(CH 3 CN) 2 (CO) 2 ]HSO 4
CH,Ctt density in the cluster . Thus many anions, generally obtained by reduction of
+ 2H 2 + 4CO carbonyl clusters in basic media (vide infra), are straightforwardly transformed.
to the corresponding hydrides by addition of protons from acids or solvents
However in the case of some high-valence cluster species substitution reac-
tions have also been observed . Thus for instance in the reaction of Re 3Cl 9 with [Fe 4(CO)12] 2 -' [HFe 4(CO) 1 3] - + H 2 Fe4 (CO),3


144 2 Transition Metal Cluster Chemistry 2-5 Cluster Reactivity 145

In many cases, by properly choosing acid and solvent, sequential protona- while in the presence of carbon monoxide, the hydrogen elimination described
tion of the anions may be achieved . above occurs .
The complexity of subsequent and secondary reactions in the protonation
of anionic clusters may be observed in the following equations that illustrate
[HOs t 0C(C0)
24 ]
the protonation of the tctraanion [Rh 6 (CO) 14 ] 4- under different reaction
conditions.

10 C(CO) 24 J 2- x- p-Toi-S0 H
[Os 6 IC01 14 ) 4-
(1 :21 3 -[Rh

H2Os 1 QC(CO)2
4
P- To(-
Sw3" - ) 2
[Rh 6 (C0) 15
[Rh6(C0)1y)h- (excess)
Similarly, the addition of acid to an acetonitrile solution of the cluster
[Ni 38 Pt 6 (CO) 4s ] 6- leads to a mixture of the mono, di and trihydrides in an
equilibrium that may be easily governed by controlled addition of acid or base . RC OOH -
_ [Rh (CO) 12
()
excess 12 30

[Ni38Pt6(CO)48] 6 H=O [Ni38PtF,(CO)48H] 5-

Cluster oxidation by reaction with Bronsted acids may also occur by ligand
[Nr38Pt6(CO)4NH2]4 [Ni3sPt6(CO)48H3] 3- elimination. Thus, species Res t stabilized in the presence of tertiary amine
CO,= M
groups in the cluster coordination sphere are oxidized by acid to Re ; +
The mono and dihydrides are stable enough for isolating crystalline salts with
Mc O ll
voluminous cations. The acidity of the trihydride prevents us,-however, from i/n[Re 3 C1,L 2 ]„ + [ LH] 2 [Re 3 C1 11 ]
obtaining pure compounds . H C'1

Protonation reactions are often complicated by further chemical trans-

formations of the unstable hydride derivatives . Thus in many instances the
reaction of anionic clusters with acids leads to oxidation products with elimina-
tion of molecular hydrogen . That occurs for example in the reaction of the anion
[Ir 6(CO) 15 ] 2- with acetic acid from which, depending of the reaction condi-
tions, two isomers of the metal cluster lr6 (CO), 6 can be isolated .
Both, ligand and molecular hydrogen elimination processes probably occur
by a similar mechanism with hydride species as intermediates . Isolation of
species like [Os s(CO)1S H 2 1] - and NMR detection of intermediates like
[Os,(CO)20 H 2 C1] - in reactions of the corresponding hydrides with iodide and
chloride ions agree with this kind of mechanism .
H 2 Os5 (CO) 1S + 1 -+ [H210ss(CO)15]
H_,Os-(CO) 20 + Cl - [H 2 CIOs,(CO) 20 ] -

Protonation and deprotonation reactions of carbonyl cluster species are in

general rather slow . A screening effect of the carbonyl groups around the metal
(Ir 6 (CO)
)2 - nucleus which makes the direct interaction of the reactants difficult is considered
t5
to be the cause of large activation barriers .
The same size effects appear to prevent the addition of other electrophiles to
r (C0) (µ 3 -CO) 4 cluster metal atoms . The attack of other nucleophiles normally leads to their
12
attachment to the ligand sphere at the high electron density point . Thus for
instance the reaction of FcCo 2 (u 3-S)(CO)y with the electrophile Cr (CO) 5 which
The elimination of hydrogen depends to a great extent upon the presence of attacks at the E0 3 -sulfur ligand may be explained .
nucleophiles in the reaction medium . Thus, the dihydride H21r 4(CO) 11 can be
prepared by protonation of the anionic monohydride in a nitrogen atmosphere, FcCo 2 (µ 3 -S) (CO) 9 + Cr(CO) STHF -Cr(CO) 5 (~t 3 -S)FeCo2(CO)9


146 2 .5 Cluster Reactivity W

2 Transition Metal Cluster Chemistry

Analogously, the coordination of main group element electrophiles normaly In liquid ammonia reduction processes are normaly drastic .
occurs at the oxygen centers of bridged CO-ligands . hq. NN,
M,(CO)12 + 6Na 3Na 2 [M(CO)4] M = Ru, Fe
Cluster Reduction Reactions . Alkali metals, sodium borhydride, and alkali hq . NN,
hydroxides are frequently used as reduction agents in cluster chemistry. Co, (CO) t2 + 3Na * 3Na[Co(CO) 4 ] + Co
Straightforward electron transfers to clusters can be often achieved by
reaction with metal atoms . Transferred electrons replace either metal-metal or Reactions Hard Bases . Cluster degradation produced by the presence of
with

metal-ligand bonds in the cluster . One example ilustrating a simple reduction CO in cluster reduction reactions may be avoided by using hard nucleophiles as
process is the reaction of the anion [Rh 12 (CO)30 ] 2- with sodium in which the OH -, OR - , or R - as reduction agents . Under such conditions oxidation of
transfer of two electrons causes the rupture of one metal-metal bond . carbon monoxide occurs leading to the formation of anionic species .

Rh 6(CO) 16 + 80H - [Rh h (CO), 4] 4 + 2C0 2- + 4H 2 0

[Rh 1 2(CO)30] 2 + 2Na zH~2[Rh b (CO) ls ] 2 + 2Na+
C04(CO)12 + 40R + 2H 2O- -[Co4(CO),1]2- + CO3 - + 4ROH

However this class of simple reductions is rather unusual . Cluster reduction
with alkali metals is almost always a rather more complex process in which the
intial electron transfer is usually folowed by degradation, condensation, or
rearrangement processes .
In the case of carbonyl metal clusters, the presence of free carbon monoxide
notoriously affects the reduction processes inducing condensations as well as
degradation of the clusters species . Thus the reduction of the tetranuclear cobalt
cluster C04(CO)4 with lithium, sodium, or potassium in which the final product
is the hexanuclear cluster [Co 6 (CO)15 ] 2- is an ilustrative example of the
complexity of such reactions .
co
C 0 4(CO)12
rxr [Co4(CO), t] - THIF [C 0 6(CO)15] 2-
Initial electron transfer induces the rupture of the metal-CO bond . The sub-
sequent reaction of the monoanion with the ejected CO produces the augmented
nuclearity_ An excess of alkali metal leads to the formation of [Co 6 (CO) 14] 4-
The formation of this tetraanion by this method is, however, not straightforward
because the anion itself undergoes degradation in the presence of carbon
monoxide :
I l [Co 6 (CO) 15 ] 2 ` + 22Na---> 11 [COI(CO)14]4- + 22Na+ + I I CO
i olation of derivatives containig groups CO 2 X from reactions of carbonyl
s
clusters with nucleophiles OR - or X - as those ilustrated in the scheme ni
Fig. 2 .55 point out to a mechanism via formyl derivatives .
M,,,(CO)„ + OH - [Mm(CO)n_ 1 (CO 2 H)] -
Mm(CO)o _ 1 (CO 2 H)] - - -~ [M„,(CO)„-,]2 + C0 2 + H +
In contrast to the reaction of [Os 5 (CO) 16 ] with the base OH - that also
produces the diaion n
Os 5 (CO) 1 6 + 20H - _ [Os 5 (CO) t 5] 2- + CO 2 + H2 O
the hig nuclearity clusters Os 6 , Os,, and Os 8 lead, under similar conditions, to
fragmentation resulting in the formation of the dianions [Os5(CO)15]2 ,
[Os6(CO),8]2-, and [Os,(CO) 20 ] 2- respectively . The diferent behavior on
reduction observed for these compounds appears to be related to the electron
structures of the clusters . Thus the cluster Os 5 (CO)16 is an electron-precise
cluster compound with six skeletal electron pairs and a regular trigonal bi-
pyramidal geometry meanwhile those of the other member of the series arc
X - / TH F
lRh 6 (C01 15 X 1 -
X= 1, Or, Cl, CN,SCN

2[Co 6 (CO) 14] 4- + l lCO----[Co 6 (CO} 15] 2 - + 6[Co(CO) 4] -

NoOR/ ROH - tRh 6 (C0) 1 5(000R)) -
Rh (CO)
Because of the 7r-acceptor properties of carbon monoxide, the tendency to 6 16 (R=Et,Me)
cluster degradation increases with increasing negative cluster charge . Therefore,
an excess of an alkali metal in a CO-atmosphere often produces the total RHN2
[Rh6(C01 t 5 (CONHR)1 _
degradation of the cluster . R= 'Pr . nBu
Na(THF)
M 4(CO) 12 + 4Na + 4CO . 4[M(CO),] - + 4Na + M = Rh, Ir Fig. 256. Reduction of reactions of Rh„ (CO), a by hard Lewis bases [Chin P, Martinego S,
CO Giordano G (1972) Gazz . Chim . Ital . 102 :330]


148 2 Transition Metal Cluster Chemistry 2 .5 Cluster Reactivity 149

electron-deficient compounds with capped polyhedral geometries . As illustrated
on Fig. 2.56, the electron-deficient Os 6, Os 7 , and Oss cluster derivatives are
transformed by ejection of Os(CO) 3 capping groups in electron-precise species
or, in the case of [Os 7 (CO)20] 2- , in one with lower deficiency than the original
neutral cluster Os8 (CO) 23 .
By using milder nucleophiles than OH - such as nitriles and halides, it is also
possible to reduce high nuclearity osmium carbonyl clusters to the correspond-
ing dianions. Thus, for instance, the reaction of Os6 (CO)18 with different nitriles
or with iodide leads to the dianion [Os 6 (CO)18] 2-
Os 6 (CO) 18 Y [Os 6 (CO) 18 ] 2- Y =I - , RCN, or P,,
The reduction in this case involves a reorganization of the metal framework
with a change of its geometry from a capped trigonal geometry to a regular
octahedral one.
Examples of the reduction of cluster species with neutral Lewis bases are also
found in the chemistry of the high-valence rhenium clusters . Thus the action of
tertiary amines on halide clusters Re 3 X9 leads to rhenium(II) cluster com-
pounds.
x2o-+
Re3X 9 + 6NR3 l/n[Re3X 6(NR 3 ) 3 ]"+ + 3R 3NHX
Reactions with Soft Bases . Metal-metal bonds are often weaker than those the
same metal can form with ligands . Thus the reaction of clusters with nuc-
leophiles frequently leads to cleavage of metal-metal bonds and to cluster
breakdown . The normally low oxidation state of metal centers on clusters makes
their reaction with soft bases such as CO, PR 3 , olefins etc. very favorable .
Clusters of lighter transition metals undergo mainly fragmentation reactions .
Heavier element derivatives however are likely to participate in addition and
substitution reactions.
Proper cluster reduction reactions can occur only when the clusters are
electron-deficient species.
Although unsaturation is a rather uncommon phenomenon there are some
examples of such compounds, for instance, the clusters (,I2-H)2 Os3 (CO), 0 and
Fe4 (CO)11 (u 4-PR) 2 which contain a total of 46 and 62 electrons respectively i .e.
clusters with two electrons less than those required by the effective atomic
number rule . As mentioned earlier in Sect . 2.3, in these cases metal-metal double
bonds are supposed to be present . This class of clusters can add several different
donor ligands to form electronic saturated species with 48 and 64 electrons
respectively.
( .t 2 -H)2Os 3 (CO) 10 + L-'H(p2-H)Os 3 (CO) 10 L
L = CO, PR 3 , P(OR)3 , CNR.
Fe4(lt 2 -CO)(CO) 10 (/14-PR)2 + L-Fe 4 (CO) 11 L(ft4-PR)2
L = CO, P(OMe) 3
As mentioned above, addition of electron donors to electronic saturated
species normally results in cluster degradation . However the presence of special
multi-bridging substituents sometimes permits the addition of neutral Lewis
bases without cluster degradation . Nonetheless the addition always implies the
rupture of metal-metal bonds . The fragments remain, however, close by the
bridging ligands . That is illustrated schematically for the reaction of the mixed-
metal cluster MnFe 2 (CO)S Cp(µ 3 -PR) with various electron donors in Fig . 2.57.
In the absence of ligands bridging the cluster structure, the addition of Lewis
bases to clusters often produces metal-metal bond cleavages inducing rearrange-
ments of the cluster metal framework . Many interesting examples of this class of
reactions are found in the chemistry of osmium carbonyl clusters . Thus, the
addition of three CO-groups to the trigonal-bipyramidal compound Os 5 (CO) 16
produces the cleavage of three metal-metal bonds yielding the cluster
Oss (CO) 14 with a "bow-tie" structure . The reaction can be reversed when
carbon monoxide is removed by heating.
R
R
P I
/ \ e~
Q

OS 6 (CO) Os 7 (C0) Os8(C0)23

18 21 Cp jM // L Cp `M/ \
~Fee ~L P L
Cp`
;r -L
~Fye~ / \ _ / -L / \
''s 'o S
L
L

(0s8 (C0)22) 2 R = Me, Et, n Bu, Ph

L = CO, PPh 3 , P(OPh) 3' AsPh 3' SbPh 3
Fig . 2.56. Reduction reactions of osmium carbonyl clusters [John GR, Johnson BFG, Lewis
J (1979) J . Organomet Chem, 186 : C69; Vargas MD, Nicholls JN (1986) Adv. Inorg . Chem . Radio Fig- 2.57 . Reactions of the mixed clusters MnFe2 (CO) 8 Cp(u3-PR) with electron pair donors
Chem 30 :123] [Sehemide J, Huttner G (1983) Chem. Ber. 116 :917]


150 2 Transition Metal Cluster Chemistry 2 .5 Cluster Reactivity 151

Oxidative Additions . Many covalent compounds (XY) such as hydrogen, halo- Table 2.26. Selected examples of oxidative additions to metal clusters
gens, mercury and silver halogenides can react with clusters resulting in an Reactions Comments Ref.
homolytic cleavage of the X-Y bond and in the oxidative addition of the two
fragments to a metal-metal bond thus increasing the formal oxidation state of Os3 (CO) 12 + H 2 - H2 0s 3 (CO) 1o + 2CO H 2 addition proceeds by 1
unsaturation achieved by CO ejection.
the metal atoms.
Y Co2 Ru 2 (CO) 13 + H2-H2Co2Ru2(CO)12 + C() 2
1 H 2 Os,Pt(CO) 1 ,PR, + H 2 -+ H,Os3Pt((,'O),,, PR, R = cyclo-C 6 H 11 . Because of 3
X-Y + -M-M- - -M-M- unsaturation in starting complex,
I addition can occur without ligand
ejection .
Os 5C(CO)1 S + H 2 -s H 2Os 5 C(CO) 15 4

This kind of reaction implies that there transfer of electrons to the

is a 053(CO)12 + X 2 - X[Os(CO)41 3 X X = Cl, Br, 1 . Product is a 5
. Therefore, if there is no cluster unsaturation before the reaction, these linear `luster,
clusters Ru5C(CO) 15 + X2 -> Ru5C(CO)15X2 6
oxidative additions will involve ligand substitution or metal-metal cleavage. H2Ru3 O 21 + 02 S) Os b(CO) 1B(u 3 -CO)(u3-O) 7
The oxidative addition of hydrogen to cluster is the best known reaction of H2Ru Sn Pro u l is open 8
this type . They are widely used for preparing hydride metal clusters . ~ HZ(CRu39(CO)O)5(SnC1(+ 3)(P3-S){)1( -CI} triangular cluster.
ster.
The electron-deficient cluster H 2Os3Pt(CO)10 P(cyclo-C6H11)3 adds one Ru 5(CO) 15 (u 5-C) + HX X = Cl, Br, Product is an opened 9,10
mole H 2 yielding the 60 electron compound H 4OS3 Pt(CO)10 (cyclo-C 6H 11 ). -HRu,(CO) 15 (X)(tls-C) cluster in which a Ru-Ru bond
to apical vertex is lacking .
This reaction which occurs under a pressure of 200 bar H 2, can be reversed in
a N2 -atmosphere. References
H2OS3Pt(CO) 10P(CyClo-C 6H 11 )3 1 Knox SA, Koepke JW, Andrews AA, Kaesz HD (1975) J. Am. Chem . Soc. 97 :3942
2 Roland E, Vahrenkamp H (1983) Organometallics 2 :183
H2 . 200 aim 3 Farrugia LJ, Green M, Hankey DR, Orpen AG, Stone FGA (1983) 1 . Chem. Soc., Chem .
---- 5 H4OS3Pt(CO)10(cyclo-C6H11) Commum ., 310
N2 4 Johnson BFG, Lewis J, Nelson WJH, Nicholls JN, Puga JN, Raithby PR, Rosales MJ, Schoder
MJ, Vargas MD (1983) 1. Chem . Soc., Dalton Trans., 2447
The H 2 -addition to the 60-electron pprecise cluster Os3 (CO) 12 yielding 6 Johnson BFG, Lewis J, Nelson WJH, Nicholls JN, Puga J, Whitmire KH (1983) J . Chem . Soc.,
H30s3(C010) appears to be preceded by formation of vacant sites on the metal Dalton Trans., 787
atoms through loss of CO ligands . 8 Adams RD, Katabira DA, (1982) Organometallics 1 : 53
9 Oxton [A, Powell DB, Farrar DH, Johnson FBG, Lewis J, Nicholls JN (1981) Inorg . Chem.
20 :4302
125 C 10 Johnson BFG, Lewis J, Nicholls JN, Puga J, Raithby PR, Rosales MJ, McPartlin M, Clegg
Os3 (CO) 12 + H 2 H2 Os 3 (CO) 10 + 2C0 W (1983) J. Chem . Soc ., Dalton Trans., 227
Further examples and reference can he found in Adams RD . Horvath IT (1985) Progr. Inorg. Chem.
Further examples of additive oxidation of hydrogen and other reagents are 33 :127; and Vargas MD, Nicolls JN (1986) Adv. Inorg. Chem . Radiochem. 30 :123
described in Table 2.26.
Analogously, oxidative additions of halogens and halides follow in general
a similar pattern to that of H 2.
The addition of HX compounds in which X has no unshared electron pairs As expected for a mechanism in which .the oxidative addition is preceded by
as it occurs in silicon and tin compounds is similar to that of H 2 i.e . one ligand elimination, light stabilized clusters add straightforwardly different sub-
CO-ligand is expelled per mol of HX . stances HX .
0s3(CO) 12 + 3HSiC13 -s(ie2-H)3 033(CO)9(SiCI 3)3
Os3(CO)10(NCMe)2-s (p2 -H)Os3(CO)1o(u2-X)
Compounds HX in which X has unshared electron pairs undergoes cluster
addition reactions yielding preferentially compounds in which X is an edge- In contrast to the H 2-addition in which the preliminary CO-ligand elimina-
bridging electron donor tion permits to retain the cluster structure, the addition of halogens occurs
preferentially through metal-metal bond cleavage without CO-elimination. This
Ru3 (CO) 12 + HX s(ic2-H)Ru 3 (CO) 10 (p2-H) mechanism which implies the formation of X - ions in a preliminary adduct


152 2 .5 Cluster Reactivity 153

2 Transition Metal Cluster Chemistry

Metal-Metal reactions are often accompanied by degradation processes, cluster rearrange-

bound cleavage Os(CO) 4 ments and coupled reactions which make it very difficult to establish the limits
0 0 between one or other type of reaction . Most redox reactions are indeed preceded
I c0 j,CO I/'c° -co ~x\ by Lewis acid-base interactions which lead to substitution products being
1I s--CO (c0) .1 *\ x/ Os
2 Co
(C 0) 3 intermediate in the electron-transfer processes .
oCo"is
c 0
x C c
0 0
Ligand Exchange in Metal Halide Clusters . Rhenium, molybdenum, tantalum
x z tx=Ct• Br and niobium halides are high-valence metal clusters that formally behave as
J
or 1)
os tCO)~
Lewis acids towards halide ions forming anionic complexes that retain the
(CO)4 0S" \ os(CO) 4 structure of the original cluster .

Os(co)4 os(co) Re 3 X 9 + 3X - -s [Re 3 X 12 ]' -

Oc\H \co -Co [M6Xs] 4+ + 6X - [ M6X14]2
M = Mo, W.
/ c0
(c o) Os \
//H\
j os(CO) 3
co [M6X1212+
+6X---~[M6X1s]`- M = Nb, Ta .
0cjsj~c
oC C4 d H r.
Anionic cluster complexes undergo ligand exchange reactions in which some
Carbon monoxide of the ligands may be easily substituted by other anionic or neutral Lewis bases .
dissoci ati on

Fig. 258. Comparison of mechanisms of hydrogenation and halogenation [Deeming AJ (1980) In : Nb6 C1 14 . 8H 20 + 4L--~(Nb6 C1 12)C12L4
Johnson BFG led) Transition metal clusters . John Wiley Chichester, p 391 ] L = Py, R 3PO, DMSO, DMF, etc. .

In the anions [M0 6 X 14 ] 2- only 6 of the halide ligands may be substituted

formation or the formation of a coordinatively unsaturated intermediate are
energetically unfavorable when X = H .
A comparison of both types of mechanism is illustrated in the scheme in
Fig. 2 .58, Further decarbonylation of the primarily reaction product leads, in
both hydrogenation and halogenation, to products with equivalent geometries
but different electronic structures .
From the point of view of the application of cluster species to catalysis
studies, oxidative addition involving the fission of C -H bonds are specially more, terminal ligands in equatorial position are exchanged more easily than
important . However most of these reactions are intermolecular processes fol-
lowing ligand exchange reactions. This theme will be therefore analyzed in
a following section after the discussion of ligand substitution reactions .
,. . .h relative facility, namely those bonded to the metal as terminal ligands . The
other 8 face-bridging ligands are, however, very inert to exchange reactions .
1
[Mo 6C1 14] 2- ->{Mo 6 Cl a }C14L2
In the case of rhenium(111) species it is also apparent that the terminal
halides are more liabile to exchange than those in bridging positions . Further-
those out of the molecular plane . Thus for Re 3 C1 9 the liability of the chloride
ions follows the series
Cl terminal in plane > Cl terminal out of plane > CI bridged

2.5.2 Cluster Reactions Without Changes in the Cluster Oxidation State 2S.3 Ligand Substitution Reactions in Carbonyl Metal Clusters

The action of Lewis bases on metal clusters leads to very many reactions . In the
last section we analyzed a series of reactions in which the addition of bases
induces different kind of oxidation-reduction processes . Nevertheless, Lewis
bases can also induce other kind of reactions which do not imply a change in the
formal oxidation state of the cluster metal nucleus . They are normally classified
as ligand exchange or ligand substitution reactions . Specially interesting are
those reactions in which the cluster structure remains unaltered in the substitu-
tion process . However, it should be also considered that ligand exchange
Although the mechanisms of cluster reactions in general have been not exten-
sively studied, there are a couple of studies dealing with the mechanism of ligand
substitution processes .
Three classes of reaction pathways may be distinguished in cluster substitu-
tion reactions :
1 . Associative mechanisms (A). The reaction proceeds through the association
of the reactants via a demonstrable intermediate in which the cluster metal


2 .5 Cluster Reactivity 155

154 2 Transition Metal Cluster Chemistry

nucleus displays a coordination number greater than in the original com- Table 2.27. Limiting first-order rate constants for the substitution reactions of Os 3 (CO)„ (NCMe)
with phosphorus and arsenic donor ligands
pound .
2 Dissociative mechanism (D) . The reaction proceeds via the dissociation of the
. 30 'c
Os3 (CO)„(NCMe) + L- Os3 (CO) 11 L + MeCN .
cluster leading to a demonstrable intermediate in which the coordination
number of the metal cluster is lower than in the original compound .
L k~,, (s)
3 . Interchange mechanism (I) . This corresponds to reaction pathways for which (average values)
the nature of the intermediate is not directly demonstrable .
PPh 3 1 .45 +0.04
Demonstration of the nature of the intermediates is in general a very difficult AsPh3 1 .52+0.04
experimental task, therefore most ligand substitution reactions are assumed to P(OPh3 ), 1 .59 + 0 .04
be interchange processes . Nonetheless, kinetic studies often permit us to estab-
lish the intimate reaction mechanism which assigns to the interchange pathways Reference
either an associative or a dissociative character . Dahlinger K, Poe AJ, Sayal PK, Sekhar VC (1986) J. Chem . Soc., Dalton Trans ., 2145
The determination of activation parameters, normally strongly associated
with the nature of the transition state complex, may also be very useful in
distinguishing plausible mechanisms in ligand substitution reactions . Dissocia-
tive mechanisms will be associated with a relatively high enthalpy change as well
as to positive ASt values . Associative processes will indeed show a not very high
endothermic effect but a considerable decrease in entropy .
Coordinatively saturated cluster compounds, specially when they are elec-
tron-precise species, undergo ligand substitutions via dissociative pathways,
meanwhile unsaturated cluster species will prefer to proceed via associative
mechanisms .
Ligand substitution reactions of the iron-group trimetal dodecacarbonyl
clusters and derivatives from them have been extensively studied . M 3(CO) 12
cluster, as it frequently occurs with stable small tri and tetranuclear clusters, is
constituted by saturated 18-electron metal atoms . Accordingly dissociative
pathways for substitutions in these compounds are expected .
L-
.
M3(CO)12 [M3(CO)t1] M3(CO)1, L Fig . 2 .59. Dependence of the first-order
rate constants of ligand substitution re-
Specially straightforward are the mechanistic studies of the acetonitrile actions of Os,(CO)„(NCMe) on the
[MeCN]/[PPh 3 ] ratio . Reproduced
derivative of the triosmium carbonyl Os 3 (CO),, (NCMe) with strong osmium- with permission from Dahlinger K, Poe
osmium bonds, inert CO-ligands, and one labile acetonitrile ligand . As men- A), Sayal PK, Sekhar VC (1986) J . Chem.
tioned in Sect . 2.4. this kind of "light-stabilized" intermediate is very useful in the Soc . Dalton Trans. 2145
synthesis of substituted derivatives .
As shown in Table 2 .27 the rate constants for displacement reactions of
acetonitrile in Os3(CO), 1 (NCMe) are independent of the nature as well as of the
concentration of the substituting ligand . The rate constants determined for the
and triphenylphosphin compete for the reaction with the unsaturated intermedi-
substitution of acetonitrile by triphenylphosphin at different ratios
[McCN]/[PPh,] illustrated in the plots in Fig. 2 .59 agree with the rate equa- ate Os 3 (CO),, .
tion . k,
Os 3 (CO) 11 (NCMe) [Os 3 (CO)„] + MeCN
.,, = 1/k, + (k-1/k,k2)[MeCN]/[PPh3)
1/k k_,

which corresponds to a single dissociative mechanism where both acetonitrile [0s3(CO)t,] + PPh3k, OS3(CO)11(PPh3)


156 2 Transition Metal Cluster Chemistry 2 .5 Cluster Reactivity 157

In Table 2 .28, the activation parameters observed for the reaction of R Fig . 2.60. Diagram for a probable
I dissociative mechanism of ligand
Os 3 (CO) 10 (NCMe) with PPh 3 as well as those obtained for substitution reac- r\ interchange reactions in M 3 (CO)9 L
tions of the trimetal dodecacarbonyls of iron, osmium, and ruthenium are / (M = Ru, Fe) [Darenbourg DJ
shown . The relatively high activation enthalpies and positive AS' values ob- rM (19901 In : Shriver DF, Kaez HD,
~M +L Adams RD (eds) The chemistry of
served in this Table agree with the dissociative mechanism described above . The M\ metal cluster complexes . VCH New
features in Table 2 .28 also reflect the much greater liability of M-L York,p17]
Os 3 (CO) 11 (NCMe) compared with Os,(CO) i2 . This probably arises from
a weaker bond strength of osmium with acetonitrile than with carbon
monoxide .
Substitution reactions of some low nuclearity carbonyl clusters such as
Ru 3(CO), 2 and lr 4(CO) 12 lead however to more complex rate constant expres-
sions than those expected for the dissociation process . Namely to expressions
containing both ligand-dependent and ligand-independent terms .

k0 =k, +k 2 [L]

An associative mechanism for explaining the second term of this rate

equation is very improbable for saturated 18-electron species without ligands
like NO, cyclopentadienyl, or arenes onto which the cluster could delocalize
part of its charge . A plausible mechanism for such a reaction could involve
metal-metal dissociations. Specially favorable for undergoing this kind of mech-
a
anism are compounds with strong face-bridging ligands that prevent major
rearrangements after metal-metal bond cleavage . In the case of the reaction 0

(u3-PR)Fe3(CO)1o-„L„ + L---* (µ3 - PR)Fe3(CO)1o-n-, Ln+,

R = aryl, L = P(OR') 3
the exchange of P(OR') 3 (L = U) L should occur via M-M bond dissociation S
as shown schematically in Fig . 2 .60. *
. •c
The M-M bond-opened intermediate of this reaction has been isolated and
identified by X-ray diffraction analysis (Fig . 2.61}.
Erg 261 . Molecular structure of (p-
t TolP)Fe 3 (CO),[PMe3]2 Reproduced
Table 2 .28 . Activation paramenters for ligand substitution reactions in some Group 8 trinuelear with permission from Knoll K, Huttner 1 .
carbonyl clusters Zsolnai L, Jibril 1, Wasincionek M (1985) J .
Organoment . Chem. 294 :91
M3L„+'sa,_

Cluster Dissociated J141 (KJ mol - ' I JS' (JK - ' mol - ')
ligand As discussed in Sect . 2 .4, the reaction of carbonyl metal clusters with N-oxide
Fe.,(CO), 2 Co 123.4 79 .5 1 trimethylamine may often be a convenient method for synthesizing cluster
Ru 3 (CO) 12 Co 133 .1 84 .5 2 compounds via ligand substitution . Kinetic studies of the substitution of CO-
Os,(CO),, CO 137 .5 31 .S 3 ligands by phosphines and arsines in group-l8 trimetal dodecarbonyls
Os,(CO)„(NCMe) McCN 112.4 92 2 4
M 3 (CO) 12 + Me 3NO + L---' M 3 (CO) 11 + Me 3 N + CO 2
References and
indicate that the formation of M 3 (CO)„ L is first order in [MI(CO)12]
I Shojaie A, Atwood JD (1985) Organometallics 4 :187
[ Me 3 NO]butzerodinhcetraionfL . One mechanism in accord
2 Poe AJ, Twigg MV (1974) J . Chem . Soc., Dallon Trans., 1860
3 Poe AJ, Sheckar VE (1985) Inorg. Chem . 24 :4376 with these features is that described in the scheme in Fig . 2 .62 . Activation
4 Dahlinger K . Poe AJ, Sayerla PK . Seckar, VC 11989) J. Chem . Six . . Daltor. Trans ., 2145 parameters obtained for these reactions are reproduced in Table 2 .29 . Moderate


158 2 Transition Meta C uster Chemistry 2.5 C uster Reactivity 159

M 3(CO) 12 + Me3NO stow (C0) M --C =O rearrangements, meta ations, igand fragmentations, e tc . in which the Os 3 s c -
2 11 3
eton is retained . However these reactions are not a ways predictab e and are
• •- ---0 often difficu t to contro . Thus for instance, from the pyro ysis of compounds of
M3N the series 0s1(CO)12 _ „(PPH 3 )„ it is possib e to iso ate and to identify the
compounds described in Fig . 2 .63 .
fast However in many instances it is not possib e to iso ate the products of
M 3 (C 0) 11 L L (CO) 1 M 3 N M e 3 + C 0 2
+
primari y substitution reactions . Thus the reaction of 0s3(CO)12 with ani ine
Fig. 2.62 . Interchange mechanism for CO-substitutions in M3(CO)I2 {M = Fe, Ru, Os} in the eads, by oss of two CO- igands, to the formation of HOs 3 (CO), o(i-N HPh) .
presence of Me 3 NO [Shen J-K, Shi Y-L, Gao Y-C, Shi Q-Z, Baso o F (1988) J. Am . Chem . Sue . Heating the products at 150 `C causes the e ection of another CO- igand and to
110 :2414 a new fragmentation of the ani ine . As i ustrated in Fig . 2.64, a competition
between two types of igand oxidative additions is observed, name y between the
addition of the other N-H bond yie ding H 2 Os 3 (CO)9 (NPh) and the addition
Tab e 2.29. Ligand substitution reactions in Group 8 trimeta carbony s. Activation parameters for of a C-H bond in position ortho to the pheny group with the formation
the dep acement of carbon monoxide by tripheny phosphine in the presence of trimethy amine oxide of H 2 OS3 (CO)9 (HNC(,H7) . This ind of oxidative addition is nown as
M 3(CO) !2 + Me 3 NO + L -, MI(CO)11 L + Me 3 N + CO2 orthometa ation .
Another examp e of orthometa ation is the series of reactions shown in
C uster L dH {KJ mot - ') 4S2 (JK ' mot-') Fig . 2.65. The therma treatment of the compound Os 3 (CO) 11 (PPh 2 R)(R = Ph
Fe 3 (CO) 12 PPh3 or Me) induces oss of carbon monoxide providing c uster unsaturation which
52 .26+2 .55 - 58 .37 ± 8 .79
Ru 3(CO) 12 PPh3 50 .67 ± 0.67 - 79 .99 ± 2 .26 promotes in turn the activation of a C-H bond in the phosphine giving fina y
Os 3 (CO) i2 PPh 3 71 .46+ 1 .21 - 24 .77 ± 4 .06 Os 3 (CO) y ( t3 -C 6 H 4)(p3-PR) . The meta ation of two carbon atoms observed in

Reference
Shen JK, Shi, Y-L, Gao Y-C, Shi Q-Z, Baso o F (1988) J. Am . Chem. Soc. 110 :2414 .
Os/
Ph/t\Ph
Ph2p~
/\ / ~ s \ PPh 3
activation entha pies and negative activation entropies agree with an associative s ~s PPh3
process .
H0s 3 (CO) 9 (PPh3) (PPh 2 C 6 H 4 ) HOs 3 (CO) 8 (PPh 3 )(PPh 2 CAH4)

25.4 Oxidative Additions Invo ving Ligand Bond C eavage

os
OS
\
Ph 2 i/ Ph 2 /
Oxidative additions may a so occur via intramo ecu ar mechanisms, often PPh 2
eading to substitution reactions . Thus, in some carbony c usters the substitu- Os O -PPh3 ~% s- =0s`
tion of CO-groups by phosphine, arsine, or ani ines originates species in which 1
the proximity of the new igands to meta c uster nuc eus often activate bonds in HOs 3(CO)7(PPh 2 )(PPh 3 )(C 6 H 4 ) HOs 3 (C0) 7 (PPh 2 )(PPh 2 C 5 H4C6H3)
the atter inducing their c eavage . The stabi ization of the products frequent y
occurs by bonding the igand fragments to the meta c uster framewor . Most
examp es of this c ass of reactions are found in the chemistry of osmium and o ` Os
ruthenium . \ Ph2 Pn 2 ` /~a Pn 2
The substitution of triosmium dodecacarbony by arsine and phosphinc /Os ~
/ p
Os ~ / s- Os~
derivatives under mi d conditions yie ds a series of simp e substitution products . I \~
Os 3 (CO) a(PPh2 )(Ph)(PPhC 6 H 4 ) Os 3(CO) 7 (PPh 2 ) 2 (C 6 H4)
Os3 (CO) 12 + nL -.083(CO)12-nLn + nCO L = PR or AsR3
Therma treatment of these products often eads to a series of processes such as Fig. 2 .b3. Examp es of compounds produced in the pyro ysis of Os3(CO),__„(PPh3)„




o

160 2 Transition Metal Cluster Chemistry 2 .5 Cluster Reactivity 161

HI •.. The orthometallation process and the possibilty of stabilzing fragments RP by

N~Osa ' bondig to the metal framework make this oxidative addition with cleavage of
ti the strong phosphorus-carbon bond possible .
0 Os These oxidative additions to Os3(CO)12 which can occur with a variety of
~H~ substrata may be described in a simple genralized way by the folowing
mil/
~ \ H20s3(CO)9(HNC6H4) equation .
Os 3[CO) PhNH2 ~H` , 150 'C
12 O53(CO)12 + H2Y-HZOs3(CO)9Y + 3C0
~os~ ;
N where HZY may be aliphatic or aromatic hydrocarbons, alkyl or aryl phophines,
Ph Ph, anilne, H2S etc ., and the products have molecular structures as those shown in
s ~H
Fig . 2.66.
\ \O Especialy interesting are oxidative additions of unsaturated hydrocarbons
os because they are the basis of many processes as hydrogenations and isomeriz-
~H ~
ations which can be catalyzed by metal clusters with similar and often better
820s3(C0)9(NPh)
results than those obtained with mononuclear catalysts (see Sect . 2.6).
Fig. 2.64. The reaction of triosmium dodecacarbonyl with anilne The behavior of metal clusters in the presenc of olefins is in genral similar
to those toward other donors . Reactions involving clusters of lighter group
elmnts normaly produce degradation of the cluster structure yielding mono-
0-S3(CO)11(PPh2R) (R=Ph orMe) nuclear compounds in which olefin double bond acts as an one-elctron pair
donor.
Fe3(CO)12 + C2F4----s(C2F4)2Fe(CO)4
Ph
A
Neverthelss, with heavier elmnts as ruthenium or osmium it is possible the
isolation of species in which the M3 framework is retained .
( _-os- -co \ / The reaction conditions necssary for the substitution of CO ligands by
Ds K olefins are often not mild enough for isolating the substitution products
I \o~i"
ilk without inducing oxidative additions processes . Thus, the reaction of Os3(CO)t 2
/

R I -benzen
I
Fig. 2.65 . Ortometallation of C-H
bonds and P-C bonds on phosphorous
substitucnts [Deeming AJ, Kabir SE,
Powel N1, Bates PA . Hursthousc M B d
a b C
(1987) J . Chcm. Soc., Dalton Trans .,
1529, Brown SC, Evans J, Smart
L (1980) 1 . Chcm . Soc ., Chem . Com- Ar
mun ., 1021 ] R
H \
®
I
this compound occurs probably through the intermediate (p2-H)Os3(CO)1o(KZ- ; ~ PR'2
P(C6H4)PhR) . As shown in Fig . 2 .65, the first metallation of the ortho-carbon os IDS IDS IDS IDS- IDS
forming an Os-C a-bond is folowed by loss of another CO group, and sub-
e f g
sequently by the interaction of the C-C double bond in the ligand with the
adjacent metal atom . As described in the same schem, the final product of this
thermal reaction is Os3(CO)9(µ3-C6H4)(p3-PR) produced by loss of benzen . Fig . 2 .66 . Examples of products r f om oxidative addition reactions of diferent substrates to
e ; (c) benzen ; (d) H2S ; (e) arylamine ; (f) anilne ; (g) alkyl or
Os .,(CO)12 : (a) Ethylen, (b) cycli olfins
aryl phosphine

162 2 Transition Metal Cluster Chemistry
-os -os
H 7~
C2H4 \ HOC \~H
-co
0s 3 (CO) 12
CO
Os 3 (C0) 11 (C 2 H 4 ) -, mss- --os!
%j
'Os~
Fig. 2.67. Oxidative addition of ethylene to Os ,(C.'O), z [Ferriar R P ; Vaglio GA,
M . Ceuni G (1972) J . Chem . Soc ., Dalton Trans ., 19981
with ethylene yields two isomers of the compound H z 0sa(v(z CO}C H 2 )
produced by oxidative addition of two C-H bonds .
Nevertheless, the intermediate substitution compounds may be prepared by
alternative ways under milder conditions .
The monosubstitution of Os 3 (CO) 12 by ethylene may be indeed afforded
using trimethylamine oxide for displacing the carbonyl group .
Os 3 (CO) 12 + Me,NO + C2H2->Os 3 (CO) 11 (C 2 H 2 ) + Me 3 N + CO2
Os 3 (CO) 11 (C 2 H 2 ) should therefore correspond to the intermediate in the
oxidative addition described in the scheme in Fig . 2 .67 . To the substitution
follow two C-H oxidative additions, both in the same carbon atom yielding the
1, 1 -disubstituted isomers A or one on each carbon forming (he 1,2-disubstituted
isomer B . The monosubstituted compound H0s 3 (CO) 10 (C 2 H 3 ) corresponding
to the product of the first C-H addition has also been synthesized by reaction of
H 2 0s,(CO) 10 with ethylene .
H20s 3 (CO) 10 + (C2"2)- .H0s .3(CO)lo(C2H3)
In the compounds involved in reaction scheme in Fig . 2 .67, the olefine is
a two electron donor in the first substitution product, three electron donor in the
second, and four electron donor in the isomers a and b .
2.6 Catalysis by Metal Clusters
The potential of metal clusters as homogeneous catalysts has been one impor-
tant component in the driving force that has permitted the spectacular develop-
ment of this chemistry observed in the last 15 years .
2.6 Catalysis by Metal Clusters 163
The nature of cluster compounds, which, as commented before, lies between
K,C/H
that of mononuclear compounds and that of pure metals, makes them specially
l attractive from the point of view of catalysis . The characteristic metal atom
distribution in clusters does indeed offer the possibility of accomplishing cata-
H\o -H lytic properties similar to those displayed by fine divided metals in many well
~~ known heterogeneous processes . However, clusters, due to their molecular
n nature, have the further advantage of displaying catalytic activity in homo-
geneous media . Actually, the metal polyatomic nuclei in cluster species simulate
H to some extent the metal surface . Thus they can, similarly to the pure metals,
~, induce changes in the chemical species bonded to them, activating processes that
C j \
often involve the rupture of highly energetic bonds . Since there is a great variety
`~
/H of homo and heteronuclear cluster species with different structures and chemical
H Os behaviours the possibilities of getting some catalysts with special properties
from such metal-like species is much greater than from the metals themselves .
b Metal cluster chemistry may be therefore specially interesting for designing
catalysts with high activity but also with a high degree of selectivity . That is
Gambino 0, Valle
specially relevant today when, because of ecological and pollution problems, it is
necessary to optimize the industrial production of chemicals diminishing ener-
getic requirements and avoiding the formation of secondary waste products .
Catalytic activity of cluster species has been detected and investigated in
a number of processes. There are some detailed studies on mechanisms involved
in such processes and many of them correspond indeed to reactions and
mechanisms described in the previous Section . However, it is in general difficult
to establish with precision which are the species actually responsible for the
catalytic phenomenon .
In order to illustrate the potential of cluster chemistry in catalysis, the
catalytic activity of cluster species in a number of selected processes will be
described . The processes to be considered - hydrogenation and isomerization of
unsaturated hydrocarbons, hydroformylation of alkenes, hydrogen reductions
of carbon monoxide, and water-gas shift reaction-arc interesting not only from
the point of view of fundamental knowledge but also because of their great
industrial and economical relevance .
2 .6 .1 The Water-Gas Shift Reaction
Hydrogen is required in copious quantities for the production of light fuels and
a great variety of other organic chemicals. Actually the production of hydrogen
for hydrogenation of hydrogen-deficient substrates, Fischer-Tropsch processes,
or ammonia synthesis is principally based on steam reforming or partial oxida-
tion of petroleum derivatives . There is however an alternative procedure for the
preparation of hydrogen, namely the reaction of coal with water at high
temperatures producing "water-gas", a mixture of H 2 O, H 2 , C0 2 , and CO .
Composition of this mixture may be governed by the water shift reaction .
H 2 O + CO 4- CO 2 + H2


164 2 Transition Metal Cluster Chemistry 2.6 Catalysis by Metal Clusters 165

Thus, after removing C02 and H2 O, hydrogen or hydrogen mixtures adequate H 4 Ru 4 (CO) 12 Fig.2 .68. Interconversion between
tri and tetranuctear ruthenium spe-
for different applications can be obtained . cies in the catalysis of the water-gas
The water-gas shift reaction may be carried out at 360'C by using the metal 0H shift reaction [Bricker JC, Nagel CC,
oxide Fe 3 0 4-Cr 2 03 as a heterogeneous catalyst . However, because of the Bhattacharyya AA . Shore SG (1985)
_ I . Am. Chem . Soc. 107 :377]
thermodynamic parameters of the reaction - AG° _ --6.82 kcal mole - !,
[H 3Ru 4 (CO) 12 ] H [HRu 3 (CO) ll ]
OH ° = -9.84 kcal mole -' and 4S° = -10.1 eu at 298 K-its efficiency and 2
thermal input requirements are more favorable at lower temperatures .
Some organometallic compounds and among them some metal cluster
carbonyls have proved to be interesting homogeneous catalysts for the water-
gas shift reaction at relatively low temperatures . Selected examples of catalysis Ru 3(C0) 12
of this reaction by cluster are described in Table 2 .30.
Detailed studies involving cluster carbonyls have been carried out with
ruthenium clusters . The catalytic effect of the cluster species Ru3(CO) 12 , However, the intermediate concentration in the reaction mixture is always low,
H 2Ru 4 (CO) 13 , and H 4 Ru4 (CO) 12 are very similar . In all these cases, whatever probably due to its high reactivity with carbon monoxide.
the ruthenium carbonyl added originally, the principal ruthenium species pres-
ent under catalysis conditions are the cluster anions [HRu3(CO),,]- and [HRu 4(CO) t3 ] - + 2CO [HRu 3 (CO) 11 ] - + 1/3Ru 3 (CO) 12
[H 3 Ru 4(CO) 12 ] - . However, the relative amount of tri and tetranuclear species
appears to depend on the relative concentration of H 2 and CO in the reaction The catalytic cycle illustrated in Fig . 2 .69 has been proposed as a possible
mixture. [H 3 Ru4 (CO) t2 ] - - which is present in the mixture only when H 2 is mechanism for the catalysis of the water shift reaction by the metal cluster
accumulated in the catalytic system - is converted in the trinuclear species by
RU3(CO)12-
reaction with carbon monoxide . This interconversion process is described in the The second step in this mechanism assumes the opening of a three-
scheme in Fig. 2 .68 . 'H-NMR spectroscopic studies on the mechanism of the center/two-electron H-bridge in the anion [HRu3 (CO) 11 ] - leading thus to the
interconversion between [H 3 Ru 4 (CO) 12 ] - and [HRu 3 (CO) 1! ] - point out to electron-rich intermediate [HRu 3 (CO) 12 ] - with an hydrogen bonded termi-
the species [HRu 4 (CO) 13 ] - as an intermediate formed by displacement of nally in a two-center/two-electron linkage as described in the reaction schemes
H 2 by CO :
.E illustrated in Fig . 2 .70. The assumption of the intermediate [HRu 3 (CO) 12] - is
[H3Rua(CO)!2] + CO -~
60 80 [HRu4(CO )13] + H2 supported by the reaction pathway inferred from kinetic studies on 13 CO- 12 CO
glyme exchange in [HRu 3 (12 CO) 11 ] .
[HRu3(12 C0)11] + 13 CO-[HRu 3 ( 13 CO)( 12 CO)1o] + 12 CO
Table 2.30. Selected examples of metal cluster catalysis of the water-gas shift reaction'

H 2O + CO . H 2 + CO2

Metal cluster Catalytic activity"

H2 Co t
Ru 3(CO) 12 2 .8 2.7
H2Ru,(CO), 3 4 .4 4.0
H,Ru4(CO) 12 3 .7 3 .3
2FeRu 3 ()
CO ,
0
Ru ( 1 12H (HRu 3 (CO)ltI -
3 103. 109
.

Ir,(CO}, 2 5 .6 6.6
Rh6(CO),6 0 .8 2+H
0
(.3 CO
Reaction Conditions : [metal cluster] = 0.012 M ; [OH - ] = 0.6 M ; [H2 0] = 6 M in 2-ethoxy- I HRu 3 (CO) t2
or
bthanol Pro = 0 .9 atm; temp. = 100 °C.
(CO)1 H - +R u 2

Reference
8.2.69. Proposed mechanism for the catalysis of the water-gas shift reaction by the
Ungerman C, Landis V . Moya SA, Cohen H, Walker H, Pearson RG, Rinker RG, Ford PC (1979) [HRu3(CO) 12] - -Ru 3 (C•O ) 11 system [Bricher JC, Nagel CC, Bhattacharyya AA, Shore SG (1985)
J. Am. Chem . Soc. 101 : 5922. J. Atn. Chem. Soc. 107 :377] .


166 2 Transition Metal Cluster Chemistry 2 .6 Catalysis by Metal Clusters 167

Ru(CO)6 R (CO) - compounds useful as fuels, as well as in chemical synthesis is especially appeal-
Fl \ k ing . Although traditionally this kind of synthesis has been carried out by using
(CO)3Ru Ru(C0) 3 + CO ~? (CV)4Ru Ru(CO) 3 heterogeneous catalysis, there is increasing interest in the development of
k-2
\ homogeneous catalysts applicable to this class of process . As mentioned before,
ti C" H homogeneous processes have in general some advantages over the heterogen-
0 1 0 eous ones. The former occurs in general under relatively milder conditions than
the latter, thus permitting better control of the properties of the catalyst and
making it possible to achieve a higher selectivity toward desired products .
Metal clusters have also proved to have great possibilities as homogeneous
Fig. 2 .70. Details of the addition of carbon monoxide to [HRu 3 (CO)11 ] - in water-gas shift reaction catalysts for the reaction of the reduction of carbon monoxide . Selected exam-
catalysis [Payne MW, Lenssing DC, Shore SG, (1987), J. Am . Chem. Soc. 109 :618] ples of catalytic hydrogenation of carbon monoxide by metal clusters are shown
in Table 2.32.
Rhodium species as Rh 6 (CO), s and [Rh5(CO),5]- catalyze the reduction of
Table 2.31. Effect of the accumulation of hydrogen on the catalysis of the water-gas shift reaction by
carbon monoxide to light alcohols, specially to ethylene glycol .
metal clusters

Cluster Conditions' Turnover" after day Mol% ruthenium species

1 3 5 [H3 Ru 4 (CO 12 ) - [HRu 3 CO) 11 ] Table 2 .32. Examples of catalytic hydrogenation of carbon monoxide by metal clusters

H 4 Ru 4(CO) 12 H2-removed` 3 .4 2.6 2.8 0 100 Cluster Products Reaction conditions Ref.
H 4 Ru 4(CO) 12 H 2 -accumulated' 3 .1 2 .0 2 .0 10 90
Ru 3(CO) t2 H I -removed' 3.8 2 .8 0 100 Os,{CO) 12 CH, (29%) ; C 2H 6 (4%) C 3Hs 180°C. 2 atm H 2 :CO = 3 :1 1
Ru 3(CO) t2 H2-accumulated" 3 .0 1.9 2.1 10 90 (20%); CH 3 Br (51%) C2H s Br solvent :liq-BBr 3 sealed glass tube
Ru 3 (CO) 12 H 2 -accumulated` - 1 .2 15 85 (13%) rate : ca. 20 turnover/h
Rh 6(CO)16 Polyols,1000 primarily ethylene 200-240 "C; 500- atm; 2, 3
' 100 °C ; 3 mol ethoxyethanol; 036
. mL H ZO ; .20 mol KOH ; [cluster] = 004 mot ; [CO] = 09
. atm .
[Rh s(CO) 1S] - glicol . MeOH . E10H, as side H 2 :CO = 1 : 1 . Activity is lower for
b Turnovers = nmol H Z (nmoI R u) compounds with hetcroatoms .
[Rh 6C(CU)is ] 2 products.
H 2 removed continuously through Pd thimble . [Rh 9P(CO}27 ] 2 High-nuclearity species appear to
H Zremoved every 24 h .
H 2 was added after day 4 and H 2 was allowed to accumulate through day 5 . [Rh„S M 1,12] 3 stable under catalysis
conditions.s.
Ir4(CO)12 C2 H ., : C''H 4 = 10 :1 (t < 3 h); Sealed glass tube 180'C 1 .5 atm ; 4
Reference
1 : 2 (t > 12 h} 12-24h ; 100% H2 : CO = 3 :1
Bricker JC, Nagel CC, Bhattacharyya AA, Shore SG (1985) J . Am. Chem. Soc. 107 :377 solvent ; molten NaCl + 3A1C13
lr4(CO) 12 After 4 h : CH, (14%), C 2H 6 Flow conditions, 175'C, 1 atm . 5
(49%), CH 3C1(32%) H2 : CO = 3 : l ; solvent; molten
NaC1 + 3A1C1 3
According to the scheme in Fig. 268. with increasing accumulation of H Z in 170180'C 1 atm 6
the reaction mixture increases the [H 3 Ru 4 (CO)12] - concentration . Experi- A-112 After ,,,, flow
3 1h and 201 Flow
atmons-
conditi
ml min - ' CH 3 (33.13%); C 2H 6 [CO] = 0 .25 atm ; solvent: molten
ments with variable accumulation of H 2 show that the number of turnovers for (57; 7%); C3 Hs (10 ; 30%) . NaCl + 3 A1C1 3
ruthenium atom increases with increasing concentration of [HRu 3 (CO) 11 ] - . C4H10 (3 ; 50%)
In Table 2 .31 some results illustrating the effect of accumulated hydrogen on 1r4(CO) 12 CH .. less than quantitative in Scaled tube; 160 180 °C; toluene 7
presence o£ P(OMe)3 . SdA
the catalysis of the water-gas shift reaction with ruthenium clusters are shown .

2.6.2. Hydrogenation of Carbon Monoxide
The catalytic reduction of carbon monoxide producing hydrocarbons, olefins,
and oxygenated compounds generally known as Fischer-Tropsh chemistry is of
great industrial and economical interest . The possibility of substituting petro-
leum by other carbonaceous sources such as coal in the production of organic
References
1 Choi H W, M utterties F L (1981) Inorg . Chem. 20 :2664
2 Vidal JL, Walker WE (1980) Inorg . Chem. 19 :896
3 Heaton BT, Strona L, Jonas J, Eguchi T, Hoffman GA (1982) J . Chem. Soc., Dalton Trans ., 1159
4 Demitras GC, Mutterties EL (1977) J . Am . Chem. Soc. 99 :2796
5 Collman JP, Brauman JI, Tustin G, Wang III GS (1983) J . Am . Chem. Soc. 105 :3913
6 Wang HK, Choi HW, Muetterties EL (1981) Inorg . Chem. 20 :2661
7 Schu RA, Demitras GC, Choi HW, Muetterties EL (1981) Inorg . Chem . 20 :4023

168 2 Transition Metal Cluster Chemistry
Polyol formation is also catalyzed by some rhodium clusters. namely
by a series of cluster species as [Rh 6 C(CO) t5 ] 2- , [ Rh 9 P(CO)2 1 ] 2- , and
[Rh„S 2 (CO)32 ]'1 containing strong bridging ligands. Because of the nature of
these ligands, they are specially appropriate for holding the cluster atoms
together in spite of possibly unfavorable electron counting. it is therefore
probable that the mechanism of such catalysis reactions involves intact rhodium
clusters.
Although most of known homogeneous reductions of carbon monoxide with
hydrogen catalyzed by carbonyl complexes produce a mixture of oxygenated cesses arise from the way the catalyst precursor is converted in either coor-
products, the iridium carbonyl species lr 4 (CO) i2 has proved to catalyze the
following homogeneous methanation reaction in toluene solutions,
3H 2 + CO---•C H4 + H2O
Mononuclear complexes are, however, inactive under similar reaction condi-
tions .
In spite of such catalytic effects of the metal cluster, the rate of this reaction
remains very low . Nevertheless, this reaction is an example of a very interesting
type of homogeneous catalysis . Here the activation of carbon monoxide appears
to be achieved by interaction of both the carbon and oxygen atoms with the
metal cluster atoms in a similar way to the CO-chemisorption on metals in
heterogeneous Fischer-Tropsch processes .
The catalytic effect of Ir 4 (CO)12 on the methanation reaction is notoriously
enhanced by the presence of strong Lewis acids, probably due to a cooperative
activation of the carbon-oxygen bond . Thus the catalysis with Ir4(CO), 2 in
a NaCl/AlCl 3 melt converts at very reasonable rate carbon monoxide and
hydrogen into light hydrocarbons, primarily ethane, without producing oxygen-
ated compounds .
Ir,(CO) 12 . A10 .1 NaCl n = 1 50- 90%
CO + 3H2 C n H2n+ 2 n = 2 10-50%
180 =C, l 2 alm
100% 12-24 h n > 2 traces
Kinetic studies of this reaction under flow conditions point out to a mechan-
ism with formation of chloromethane as reaction intermediate . Nonetheless, as
observed in Table 2 .32, the results are strongly affected by the conditions of the
experiments . Temperature appears not to affect the product distribution very
much but this is dramatically influenced by contact time . The variety of product
distributions as well as discrepancies in possible intermediates inferred from
diverse investigations could be also explained by different catalysts arising from
the same precursor .
The catalysis of hydrogenation of carbon monoxide with Os 3 (CO) 1 2 as
catalyst precursor also produces a mixture of hydrocarbons with high methane
content . Moreover, in this case, the formation of bromine derivatives is
observed . During the catalysis, however, Os 3 (CO), 2 is converted into
a halogenated dinuclear species which appears to
be the enduring catalyst .
2 .6 Catalysis by Metal Clusters 169
2.6 .3 Olefin Hydrogenation and Isomerization
Hydrogenation of unsaturated hydrocarbons is a process of great economical
importance . Many transition metal cluster species have displayed interesting
catalytic effects on such kind of reactions . Selected examples of hydrogenation of
olefins are described in Table 2 .33 .
As it can be appreciated in Table 2 .33, there are different kinds of hydrogen-
ation and isomerization reactions . Fundamental differences between these pro-
dinately or electron unsaturated species able to interact with the olefin begin-
ning thus a catalytic cycle .
Thermal Activation . As often discussed in previous sections, metal clusters, in
general, undergo relatively easy thermal decomposition with carbon monoxide
ejection . From these reactions highly reactive coordinately unsaturated derivat-
ives which can he active catalysts arise .
A relatively simple example of this class of cluster catalysis is the hydrogen-
ation of ethylene catalyzed by the tetranuclear ruthenium cluster H 4 Ru 4 (CO)12
described by the following equations .
H,Ru a (CO), 2 K, a Rua(CO)t I + CO
* H
K,
H,Ru,(CO) 11 + H2 - H ( Ru 4 (CO) 11
H,Ru,(CO) 11 + C2H 4 H3Ru4(CO)11(C2 1-I5)
H3Ru,(CO)11(C2H5) + H 2 --- . H6Ru4(CO)11 + C2H6
Kinetic studies of this process do indeed show the catalysis being first order in
the concentration of the ruthenium cluster and inversely dependent on the
partial pressure of carbon monoxide indicating thus that the most important
intermediate in the reaction is the coordinately unsaturated species
H 4 Ru 4 (CO) 11 . Coordinately unsaturated sites in the catalyst would be achieved,
in this case, by the dissociation of a CO-ligand . The catalytic effect of the
unsaturated intermediate depends on the reversible insertion of ethylene into the
Ru-H bond . However there is competition between this insertion and the
, addition of carbon monoxide or H 2 for obtaining the starting compound or the
hexahydride H 6 Ru4 (CO)1 , respectively .
The hydrogenolysis of the ethyl group in H,Ru a (CO) 1i (C2 H5) closing the
catalytic cycle is the rate-determining step in this process .
Photochemical Activation . An alternative way of inducing the formation of
coordinately non-saturated species able to participate in catalytic processes is
the selective displacement of CO-ligands by photolysis . The mechanism of
addition of H 2 to ethylene catalyzed by H 4 Ru 4 (CO),2 is similar to that for


Table 2.33 . Selected examples of catalytic hydrogenation by metal clusters

J
0
Metal Cluster Reaction Type/ Catalysis Reaction conditions and catalysis activity Ref.
Hydrocarbon activation
N

Fe 3 (CO), 2 Isomerization -I
Photochemical 25'C, 30 s laser irradiation, 515 rim . [Fe], = 5 x 10 - ' M. 1 w
I-penteme [R] = 9 .14 M (neat) ; rate : 900 turnovers min -1
H,Ru,(CO) 12 Hydrogenation Thermal 72''C; PIH 2) = P(C2 H 4 ) = l00. 2
C 2 H,
H4 Ru 4(CO), 2 Hydrogenation Photochemical 25'C ; irradiation 366 nm, ca . 10' einstein min - ' ; 3
C2H4 P(C 2 H 4 ) = P(H 2 ) = 0 .13 bar [Ru 4] = 10 - ' M .
H4 Ru,(CO), 2 Isomerization Photochemical -'
25 `C; 2h irridiation 355 rim, ca . 1 .2x 10 einstein min - ' ; 4
1-pentene [Ru 4 ] = 5 x 10 -4 M [R] = 2M ; rate : 250 turnoverr h - 1 ; trans-to
cis- 2-penetene isomerization ratio = 1 .8.
[HRu 3(CO) 11 ] - Hydrogenation Anion-promoted 25 C, dimethyipropylene, formanide ; [Ru 3 ] = 0.25 mmol .
1 5
[R] = 0,06 mol, [H 2 ] = 20 bar; rate: 0.3 turnover min '
Ru 3(g3-NPh) 2 (CO) 2 Hydrogenation Thermal 98 = C ; heptane ; [Ru 3] = 7 x 10 ' mmol [R] = 0 .35 mmol, 6
3,3-dimethylbutene [H 2 ] = 3 bar ; rate : 0 .5 turnover min - '
H 2 Ru 3 (CO)9 (u 3 -PR) Hydrogenation Ligand-assisted 61)"C ; [R = Ph] = 9 mmol ; [H 2 ] = 60 bar ; rate : ca . 2 turnover h - ' 7
styrene
[Ru 3 (y 2 -NCO) (CO) la] Hydrogenation Anion-promoted 25 'C, [Ru 3 ] = 1 .4 mmol, [R] = 0 .38 mol . [H 2 ] = 0.74 bar 8
H 3 Ru4{Au(PPh 3 )j' (CO), 2 Isomerization
1-penetene Ligand effect 35'C; CH 2 C1 2 ; [ Ru 4 Au] = 2 mmol, [R] = 54 mmol, [H,] = 1 atm ; 9
trans to cis-penetene ratio: 2 .8 (after 24 h); rate : ca . 20 turnover d - '
NiRu 3(p-H) 3 (CO)9(Cp) Hydrogenation
1 .3-pentadiene Thermal 120'C; n-octane, cis-1,3-pentadiene ; [NiRu 3] = 1 .7 x 10 -4 M, 10
[R] = .210 M ; products ( °fin): pentane (1 .4): 1-pentene (7 .3), truns-
2-pentene (18 .4), cis 2-pentene (13.1); rate: 11 .3 turnover min '
H4Os4(CO)I2 Hydrogenation Thermal 114() 'C; [Os4 ] = 0 .112 M. 11 estyrene [R] = 1 .2 M. I1
styrene [H 2] = 1 .05 bar; rate: 1 .45 turnover min '
H 2 Os 3 (CO), o 1-hexene Unsaturation 50 °C ; octane; [H 2 ] = 3 .4 bar ; [Os 3 ] : [hexane] ~- 1 : 1 W; 35 h; rate : 12
I turnover h -1 .
[Os 3 (NCO) (CO) 11 ] - ' Hydrogenation maleic Anion-promoted 60'(' ; [H 2 ] = 3 .4 bar ; 3 equivalent succinic anhydride are produced 13
anhidride anion after 24 h

Hydrogenation Ligand-assisted 20°C, toluene; [Rh2] - 0.02 mmol, [H 2] = 0 .8 bar ; rate : ca. 14
((Jr-H)Rh[P(O-i-C3 H 7 )3]2 f 2
2-butyne 1 turnover min -1 ; reaction totally selective to trans alkene ; catalyst
life-time: 5 min
20°C ; product : cis-stilbene 15
Ni4[CNC(CH3)3]7 Hydrogenation Ligand effect
diphenylacetylene

References
I Mitchener JC.Wrighton MS (1981) J . Am . Chcm . Soc . 103
:975
2 Doi Y, Koshizuka K, Keii T (1982) Inorg. Chem . 21 :2732
3 Doi Y . Taniura S, Koshizuka K (1983) J . Mol Catal . 19 :213
4 Graft JL, Wrighton MS (1980) J . Am . Chem . Soc. 102 :2123
5 Sam-Fink G, Reinr J (198211 Mol . Catal . 16 :231
6 Smieja JA, Gozum JE, Gladfelter WL (1986) Organometallycs 5 : 2154
7 Mani D, Varenkamp H (19851 J . Mol . Catal . 29 : 305
8 Zuffa JL, Blohm ML, Gladfelter WL (1986) J . Am . Chem. Soc . 108 : 552
9 Evans J . Jingxing G (1985) J . Chem . Soc., Chem. Commun ., 39
10 Castiglioni M, Giordano R, Sappa E (1987) J . Organomet. Chem . 319 : 167
11 Sanchez-Delgado RA, Andriollo A, Puga J, Martin G (1987) Inorg . Chem . 26 :1867
12 Keister JB, Shapley JR (1976) J . Am . Chem . Soc . 98 :1056
13 Zuffa J), Galdfelter WL (1986) J . Am . Chem . Soc . 108 :4669
14 Burch RR, Shusterman AJ, Muettertier EL, Teller RE, Wiliams JM (1983) J . Am . Chem. Soc. 105 :3546
15 Mutterties EL, Band E . Kokorion A, Pretzer WR, Thomas MG (1980) Inorg. Chem . 9
:1552


172 2 Transition Metal Cluster Chemistry 2.6Catlysi bMetalCuster 173

thermal activation discussed above but in which the substitution of the CO Fig, 2.71.Catlysi mechanism by unsaturated
cluster species. The reaction of H ZOs 3(CO),,, with
group by the olefin is activated phot chemical y . alkenes [Keister JB, Shapley JR (1976) J . Am.
Chem . Soc. 98 :1056]
H4Ru4(CO) 12 + L h` > H4Ru4(CO) 11 L + CO

In this case the rate determining step of the reaction is again the oxidative
addition of H2 . Thus, for instance, the photolytic ad ition of 1-pentene to the
cluster H4 Ru4(CO)12 leads to olefin isomerization with reaction rates of ca . 2000
turnovers per hour at 25 "C . The hydrogenation rate howev r is considerably
lower. Thus with an increase in the H 2 pressure of 6 .89 -101 Pa in the same
sy tem a rate of only 60 turnovers per hour is achiev d .Theyildintermsof
isomerization cy les per photon is notoriously high, about 30 turnovers per
alkene
photon . An an log us behavior is observed in the isomerization cat lyzed by

\ . 4&
~~ Fe h(GO)12 /

Fe3(CO)12 where a laser irradiation of 30 seconds originates an isomerization

rate of about 10 3 turnovers per minute. That is one of the most rapid among
known proces es in homogeneous catalysis . However in this last case, contrast-
ing to the isomerization with H4 Ru4(CO)12 , the reaction occurs via metal-metal
bond cleavage.

Fe3(CO)12 hU 3 Fe(CO) 4

In general, the photolytic activation of clusters is easier than that of the

equivalent mononuclear species because the former absorbs energy at lower
frequencies, often in the visible spectrum .

Electron Unsaturated Catalyst Precursors . As an lyzed in previous Sections, the

trinuclear cluster H 2Os 3(CO)10 isanelctronicalyaswel ascordinately
unsaturated species . The hydrogenation of olefins in the presence of
+ oletion
H 20s3(CO) ta thusconstiuesatypicalexmpleofcatlysi nduce byintr - 0 ~-
sic unsaturation of the catalyst precursor C
. In thes case , the activation en rgy N
for the formation of the complex cat lyst-substrate is rather low . The mechan-
Fig. 2 .72. Olelin hydrogen-
ism proposed for this kind of catalysis is il ustrated in the scheme in Fig . 2.71 . ationcatlysedb[Ru3(p2 -
NCO)(CO),,,J . [Zuffa JL,
Anionic Cat lyst Precursors . Excel ent results in the hydrogenation of olefins Gladfettcr WL (1986) J . Am .
are obtained by labilization of the cluster by the formation of anionic species Chem . Soc. 108 : 4669]
. As
discussed in Sect . 2.4.2, this method is often used for the activation of clusters in
substitution reactions .
The anionic cluster [Ru 3 (p 2 -NCO)(CO) 10] - catlyzesth ydrogenatio f mechanism proposed for this reaction is illustrated in the scheme in Fig . 2.72
olefins with reaction rates of ca . 5 turnovers per minute at room temperature . which as be n confirmed not only b kinetic investigations but also by the
Ac ording to kinetic studies, the determinant reaction step is the oxidative synthesis and crystal ographic characterization of the intermediate species
ad it on of hydrogen to the anion [M 3(CNO)(CO)9] - (M = Ru, Os). The [HOs 3 (NCO)R(CO)9] - withR=sucinoylahdrie . Similar studies with the


174 2 Transition Metal Cluster Chemistry 2.6 Catalysis by Metal Clusters 175

ruthenium derivatives has been not possible because of considerably higher stereo selectivity is privative of the dinuclear compound . The catalysis by
rates of the catalytic processes . mononuclear species used directly or from the degradation of dinuclear com-
pounds gives rise primarily to the cis-isomer .
Special Ligunds. As discussed in Sect 2 .5 .3, the substitution of carbonyl ligands
in the cluster often enhances the liability of the clusters . This property has also
been used in catalytic processes . Thus for instance, the nickel cluster with 2.6.4 Hydroformylation
isocyanide ligands Ni 4 (CNR), is an efficient catalyst precursor in the hydrogen-
ation of acetylenes. Actually, Ni 4 (CNR) 7 reacts with acetylenes yielding the Reactions of simultaneous addition of carbon monoxide and hydrogen to
adduct Ni 4 (CNR) 4 (acetylene) 3 which in turn is able to catalyze, under rather olefins leading to carboxylic compounds arc known as hydroformylation
mild conditions, the hydrogenation of diaryl and dialkylacetylenes at rates of ca . reactions .
one turnover per minute . Mononuclear complexes do not catalyze this reaction
under the same conditions . C = C + CO + H 2 - H-C-C-CHO
This class of reaction is specially interesting in the conversion of hydro-
H,
RC-CR cis RHC=CHR carbons in compounds with functional groups useful as material for organic
Ni4[C'N(CH,),1a[Natj') PhC-CPhI,
synthesis . Cluster compounds have also proved useful in the catalysis of this
The hydrogenation of acetylenes catalyzed by the dinuclear compound kind of process . Selected examples of this kind of catalytic hydroformilation are
1HRh[P(O - i_C3H7)3]2)2 is an interesting example of stereo selective cluster shown in Table 2 .34.
catalysis . At 20'C acetylenes arc transformed into trans-alkenes with a rate of In many cases, olefin hydrogenation reactions lead under relatively more
1 turnover per minute in a totally stereo-selective reaction . The mechanism drastic conditions, and in the presence of carbon monoxide, to the hydrofor-
proposed for this process is illustrated in the scheme in Fig . 2.73 . This kind of mylation of the olefin . Thus, for instance, the cluster hydride [l-IRu,(CO) t t ] ,
which as discussed above catalyzes under mild conditions (25 °C, 20 bar H 2 ) the
s hydrogenation of ethylene, leads, at higher temperatures and in the presence of
carbon monoxide, to the formation of propanal according to the scheme
P H P + H P` H P
~Rh~ \Rh /+H Rh I"HRh
\ / H illustrated in Fig. 2 .74 . The mechanism involved in this scheme agrees with the
2
P 11 ~H~ ~p -H ,k -1 P~ '_1 H~ P isotopic distribution observed in propanal by using molecular deuterium D 2 .
k Preferential deuterations of the formy] hydrogen (9$%) as well as of one
RC `CR RC = CR
((oss of H 2 }
R Table 2.34 . Selected examples of catalytic hydroformylation of olefines by metal clusters .
I Reaction conditions Ref.
C R Metal Cluster Olefin
I`/ ~
P~ R~C~~ P [HRu,(CO)„] ethylene 100 C ; [CO] = 2.6 bar; 1
[H 2] _ [ C2H4] = 13 bar; rate : I turnover
P/ per min .
H 'R \P
I pentenc 90"C ; [COl = [H 2] = 57 bar; 104 h ; 2
k Co3(CO)9(/l3-C.Ph)
4 57 .5% ; selectivity = 5 .4.'
2 pentenc 110'C;[COi = [H 2 ] = 30.6 bar ; 775 h ;
99.8% ; selectivity = 1 .0 .
H Co 3(CO)„ (p,-CO) : (/2 4 -PPh)2 1 pentene 130 - C; [CO] = [H 23 = 57 .8 bar : 2

c.
\ iR
23 h ; 100% ; selectivity = 2.7 .
P~ ,P 2 pentene 130'C ; [CO] _ [H 23 = 32.3 bar ; 72 h ;
Rh "Rh
P~ 'H' ~, P 87 .7%; selectivity = 1 .2.
Fig . 2.73 . Hydrogenation of al-
H2 1 k5 kynes to trans-alkencs catalysed ' Selectivity : Product distribution ratio of Normal : Branched hydrocarbons .
by ( ( /2 -H)Rh[P(O - i -C1H7)3l2)2
trans-alk ene [Burch RR, Shustcrman Al, References
Muetterties EL, Teller RG, Will .
lams JM 11983) l . Am . Chem . Soc. I Suss-Fink G 11980) J . Organumet . Chem . 193 : C20
(HRh P2 ) 2 2 Ryan RC, Pittman Jr, CU, O'Connor JP (197711 . Am . Chem. Soc., 99 :1986
105 :3546]


176 2 Transition Metal Cluster Chemistry

-1-

Fig. 2.74. Catalytic hydroformylation of ethylene by [HRu3(CO)„]- [Suss-Fink G, Hermann

G (1985) J . Chem . Soc., Chem. Comm un ., 735]

C H0

CHO

Fig . 2.75. Selectivity in hydroformylation of I and 2-pentene [Ryan RC, Pittman Jr . CU, O'Connor
JP (1977) J . Am . Chem . Soc . 99 : 1986]

hydrogen in the methyl group (7a 80%) are observed, meanwhile the methylene
group shows low deuterium incorporation (5-12%) .
As analyzed in a previous Section (see Sect . 2 .4 .5), there are some clusters
containing strong face-bridging ligands which have the property of holding to
cluster structures in spite of cleavage of the metal-metal bonds arising for
instance from an excess of cluster skeleton electrons . This property may also be
useful for cluster catalyst precursors.
The cobalt clusters Co,(CO),,(p3-CC,,H,) and Co4 (CO) 8 (p 2-CO)2
(u 4 •P C h H s )2 also catalyze . under mild conditions, the hydroformylation of l-
and 2-pentene to aldehydes in relatively high yields . Moreover, this process can
be achieved with a fairly high normal-to-branched selectivity (Fig . 2 .75) . The
clusters are recovered unchanged with high yields from these reactions and the
hydroformylations are performed at milder conditions than those required for
the catalysis with Co 2 (CO) R . These features point out to catalysis by the intact
clusters, assisted probably by the presence of the strong bridging ligands . The
effect of the tigands is specially strong in the case of the phosphinidene com-
pounds Co4 (p 4 -PPh) a (CO) t o with two bridging ligands .