CHAPTER 9 METAL CLUSTER COMPLEXES

Objectives: In this unit, we study co-ordination complexes with many metal

ions.

INTRODUCTION When sample apparently simple compounds are

examined carefully using X-Rays techniques, they are found to contain two or
more metal ions held by direct metal metal-bonds . Compounds with metal
bonds are commonest among compounds of metallic elements which form
compounds in several oxidation states . They are particularly common among
early d-block elements when they occur in low formal oxidation states .

[,If you find some

OCCURRENCE OF METAL-

repetition , it is because the edtiting is

not complete )
As noted in the introduction metal-metal bonds are common among metals
which form different oxidation sates and the metal is in a low formal oxidation
state.
Example 1. The dimercury cation , [Hg-Hg]2+.
Mercury in formal oxidation state+1 exists as the dication [Hg-Hg] 2+. Hence,
the correct formulation of the mercury(I) halides is Hg 2X2 (X=Cl, Br, I) rather
than HgX .

FORMATION OF METAL CLUSTERS

Whereas formation of metal clusters occurs even among fairly soft metals such
as mercury, it is actually common among the transition metals and especially the
early d-block elements in the 4th and 5th periods. These elements have high
melting points and high boiling points . Elements in which the atoms are held
together very strongly require very high temperatures to melt or boil.
Let us assume for a moment that we are able to see the individual atoms on a
block of a metal such as the one displayed in figure 9.1 . The individual atoms
that form such a solid must be held together by some forces of attraction,
otherwise , the solid would not exist as such !!!
Let us now focus our attention on one of such atoms.
An important question that comes to mind is: How much energy is required to
dislodge such an atom from the others and take it to an infinitely large distance ,
r∞, to a point P such that the attraction of this atom by the rest of the solid is
negligible?.
Figure 9.1 Atoms on the surface of metal solid

r P

It should further noted that this is not a trivial question. A lot effort has been put
in estimating this energy . Some aothors actually refer to it as sublimation energy.
“Enthalpy of atomization” (or using the alternative terminology
..Sublimation Energy) is defined as the energy needed to dislodge an atom from
a solid element and take it to infinity”. By infinity we mean a point P, some
distance r∞ such that the attraction of this atom be those left on the solid is
negligible. The enthalpies of atomization for the alkali metals and the alkali earths
are tabulated are tabulated in Table 9.1 and for comparison purposes , those for
the d-block elements are tabulated in Table 9.2 .

Tables 9.1 Enthalpies of Atomization of Alkali Metals and Alkali Earths .

Atomic Number,Z. The Values are in kJ/mole
(3)Li (11)Na 73.6 (19)K (37)Rb 45.6 (55Cs 44.7
106.5 57.3
(4)Be (12)Mg146 (20)Ca (38)Sr 164 (56)Ba178
324 178

ENTHALPY OF ATOMIZATION FOR d-BLOCK

ELEMENTS

The Values are in kJ/mole

(22)Ti..469 (23)V510 (24)Cr 397 (25)Mn 281 (26)Fe (27)Co (
398 425 4
(40)Zr 612 (41)Nb (42)Mo (43) Tc (44) Ru (45) (
724 664 640 Pd556 P
(72)Hf 612 (73)Ta782 (74)(W)849 (75)Re(779) (76)Os (77)Pt (
791 669 6
A comparison of the data in Tables 9.1 and 9.2 shows clearly a very large
difference in the enthalpies of atomization .

Examples of transition metal compounds which contain metal cluster complexes .

(a) Dihalides of Group 6 Elements namely chromium, molybdenum and
tungsten.

When chromium is reacted in a limited amount of chlorine or bromine , the

dihalides CrCl2 and CrBr2 are formed. These dissolve in water to form hydrated
compounds of the type CrX2.6H2O which behave exactly like CaCl2 . Thus , just
as dissolution of CaCl2 gives the ions , [Ca(H2O)6]2+ , the chromium halides also
give the cationic aqua complex , [Cr(H2O)6]2+ . This means that 100% of the
halides are ionized just as in the case of CaCl 2 or CaBr2. In contrast to this, when
compounds with the empirical formulae MoX2 (X=Cl, Br) are dissolved in water
, only a third of the halides are ionized . X-Ray structure studies of these solids
shows that the compounds should be formulated as Mo 6X12. They contain metal
cluster complexes of the type [M12X8]4+ with the structure shown in Figure 9.2.

Figure 9.2 The Structure of the [M6X8]4+ metal Clusters

M Key
= A covalently bonded halide ion at
M
M centre of each face

M
M M =Metal ion at each corner
of a regular octahedron
M

Note: Clusters of this type are found in all the halides of the general formula
MX2(M=Mo, W;X=Cl, Br, I).
This tendency to form metal clusters is also observed in molybdenum and
tungsten halides of the type, MX3(M=Mo,W; X=Cl, Br, I) . These are formed
when the metals are heated in limited chlorine or bromine in moderately low
temperatures.
As is the case with halides of the type, MX2, when the halides MX3 are dissolved
in water, only a third of the halogens is ionized . These have the molecular
formula, M6X18. The reason for ionization of only a third of the halogens is that
these halides contain the metal cluster complexes of the type, [M 6X12]6+, with the
structure shown in structure shown in Figure 9.3
Figure 9.3 The Structure of M6X12clusters
M
Key
M
M
= halide ion
M
M =Metai ion
M

M=, Zr2+, Zr3+, Hf2+, Hf3+, Hf3+ ; M=Nb2+, Nb3+, Ta2+,

Ta3+, Mo3+, W3+

These clusters occur in all the halides of the general formula M 6X18
(M=Mo,W;X=Cl, Br, I).
2. The metal cluster complexes have the general formulae, [M 6X12]6+ which has
the following features :-
(i)The metal Cluster , [M6X12]6+ in which there are six metal atoms at the corners
of a regular octahedron(Figure 9.3).
(ii) There are direct metal-metal bonds between the various atoms .
(iii)There is a covalently-bonded halogen along each edge of the octahedron.
(iv) Finally, we note that this cluster is common in :-
(1) All The halides MX3(M=Mo,W; Zr, Hf, Nb, Ta,; X=Cl,, Br, I))
(2) All The halides MX2(M= Zr, Hf, Nb, Ta, X=Cl,, Br, I)
(3) Some non-stoicheometric Zr, Hf, Nb and Ta compounds such as Nb 6Cl14.

Examples of Other Metal Halide Clusters. The Tendency to form clusters is

exhibited by niobium, tantalum, molybdenum and tungsten even when these
elements are in formal oxidation state +4 especially with Cl, Br, and I
compounds.

Thus the simple formulae , MX4(M=Nb, Ta, Mo, W;X=Cl, Br, I) tell a reader
nothing about the true nature of these compounds. X-ray Stucture determination
shows that , these have the general structure , shown in figure 9.4
Figure 9.4 Structure of the Tetrahalides , MX4

(M=Nb,Ta,Mo,W, ;X=Cl,Br, I)

X X X X X XX X X X X X X
X
M M M M M M M

X X X XX X X X X
XX X X
And ,as can be seen, they contain long chains joined by metal-metal bonds. In the
tetrahalides MX4(M=Nb, Ta;X=Cl, Br, I) , the central metal ion has one electron
in a d-orbital. Unlike the chromium halides CrX4(X=Cl,Br) the niobium and
tantalum halides are diamagnetic because the electron in the d-orbital is used for
formation of the metal-metal bond.

Examples of Other Metal Cluster Complexes.

(i) Halo species of Molybdenum(III) and Tungsten(III). The
octahedral molybdenum(III) and tungsten(III) species of in
[M6X12]6+ clusters have already been noted. Both
molybdenum(III) and tungsten(III) also forms clusters of
other types . particularly notable are dinuclear species of the
type, M2X9]3- (M=Mo, W; X=Cl, Br) . These have the structure shown in Figure
9.5

Figure9.5 The Structure of the Dinuclear Complexes, [M2X9]3-

3-
X X X Key
XX M M X
X
M=Mo, W; X=Cl, Br)

XX

(ii) Some halo species of Rhenium(III).

 Rhenium forms all the halides with empirical formula ReX 3(X=Cl, Br, I).
These are metal cluster complexes which should be formulated as , Re 3X9(X=Cl,
Br, I).They have the general structure shown in Figure 9.6

Dinuclear species are also known where neutral molecules are co-ordinated to
metal atoms. The Group7 metal carbonyls M 2(CO)10(M=Mn, Tc, Re) (fig.8.2) are
typical examples .

Fig 8.1 Dinuclear Metal Clusters of the type, [M2X9]3- Fig 8.2 Dinuclear Metal Carbonyl , M2(CO)9
(M=Ru, Mo, W,
CO

CO
(M= Mo, W,
O
C CO
OC
CO
OC
CO
Metal-Metal bond OC Metal-Metal bond

C
O
Metal ion Metal atom (M=Mn, Tc, Re)

The anion

The cobalt carbonyl Co2(CO)8 and the iron carbonyl , Fe2(CO)9 are also
dinuclear with structures similar to that of the manganese group carbonyls the
only difference being that in the cobalt carbonyl, two carbonyls are used for
bridging (i.e a carbonyl group is bonded to two metals) and in the iron carbonyl,
Fe2(CO)9 ,three carbonyl groups are bridging.
Trinuclear species. The rhenium(III) halides with the empirical formulae,
ReX3, (X=Cl, Br, I) have molecular formulae, Re3X9 (X=Cl,Br,I) and have the
general the structure shown in figure 8.3. When such halides are fused with alkali
metal halides , anionic species of the type, [Re3X12]3-,(X=Cl, Br) are obtained.
Tri-nuclear Metal clusters also occur between neutral metal atoms and

Fig 8.4 Structure of the Metal Carbonyl,

M3(CO)12(M=Ru, Os)
Fig 8.3 Structure of the Trinuclear Rhenium Halides, Re3X9
CO
CO

CO

OC CO
OC CO
CO

C
O C CO
OC
O
=Metal Ion = Metal atom

=Halide Ion

Neutral molecules( see figure 8.4 above).

Tetranuclear metal clusters. Molybdenum, niobium and Tungsten form well –
established tetranuclear clusters . Thus, both molybdenum and tungsten form
tetranuclear clusters of the type, M4X8L4 ( M=Mo, W, X=Cl,Br; L=neutral ligand
such as a tertiary phosphine . An example of such a complex is shown in figure
8.5 . Tetranuclear complexes are also known in metal carbonyls. Ir 4(CO)12
(Figure 8.6) is an example of such clusters.

Fig.8.5 Tetranuclear Complexes of the Type M4X8L4

(M=Mo, W; X=Cl, Br, L=Tertiary Phosphine

Fig.8.6 Tetranuclear Iridium carbonyl

L L Ir4(CO)412

CO
CO
CO

CO
oc CO
CO
oc CO
L L
oc CO
CO
=Rh, Ir
= Ir

Pentanuclear Clusters. Again, these are best illustrated by metal carbonyls. Figure
8.8 shows a pentanuclear osmium carbonyl.

Figure 8.7 A Pentanuclear Metal carbonyl

CO
CO

O
C

CO CO
CO
CO
CO =Osmium atom
CO
CO
CO
C
O

CO
CO
CO
OCTAHRDRAL METAL CLUSTERS . These are common in halides formed
by transition metals with high enthalpies of atomization and especially when a
metal is in a low formal oxidation state. The property is commonest among the
early d-block elements on 2nd and 3rd transition series . These elements have
relatively high enthalpies of atomization in comparison with the other elements.
Two common examples are clusters of types [M6X8]4+ and [M6X12]6+ . ,
(a) The [M6X8]4+ complex cation .
When all the molybdenum(II) and tungsten(II) halides of the type, MX 2(M=Mo,
W;X=Cl, Br, I) are dissolved in ionizing solvents , it is found that only a third of
the halides is ionized. Structural study of these halides shows that , there is an
octahedral cluster M6 with a halogen at the centre of each face. This halogen is
covalently bonded to the three metal atoms on that face. It is for this reason that
halides of these elements which appear simple are actually metal clusters. For
example, when MoCl2 is dissolved , only a third of the halogens is ionized.

Figure 8.8 The Structure of

Figure 8.7
M6X12clusters
The Structure of the [M6X8]4+ metal Clusters

M M
M M
M = halide ion
M = halide ion
M M M =Metai ion
M M =Metai ion M
M
Note a covalently bonded halogen at M
the centre of each face of the
octahedron.
M=, Zr2+, Zr3+, Hf2+, Hf3+, Hf3+ ; M=Nb2+, Nb3+, Ta2+,
[M6X8]4+ (M=, Mo,,W; ,X=Cl, Br, Ta3+, Mo3+, W3+
I)

This cluster is common in the following

is dissolved in water, only a third of the halogens are ionized.

Further Reading: FA Cotton and R.A Walton . Multiple Bonds between Metal
Atoms. Claredon Press. 2nd Ed.1993.
 The Structure of the [M6X8]4+ metal Clusters
This cluster is common in the following

M [M6X8]4+ (M=, Mo,,W; ,X=Cl, Br,

= halide ion I)
M M=Metai ion
M
M Note a covalently bonded halogen at the
M centre of each face of the octahedron.

The Structure of the [M8X 12]6+ metal Clusters

This cluster is common in the following
M
n
[M6X12]
M = halide ion
+
M M =Metai ion M=, Zr2+, Zr3+, Hf2+, Hf3+ b3+, Hf3+ ; M=Nb2+, Nb3+,
M
M Ta2+, Ta3+, Mo3+, W3+

M
The halides are Cl, Br or I

Metal clusters are very common in halides of early d-block

elements on 2nd and 3rd transition series . especially when the
element is in a low formal oxidation state because these
elements have relatively high enthalpies of atomization in
comparison with the other elements. It is for this reason that
many halides of these elements in low formal which appear
simple are actually metal clusters. For example, when MoCl2
is dissolved , only a third of the halogens is ionized.

is dissolved in water, only a third of the halogens are ionized.

Fig 8.2 Dinuclear Metal Clusters of the type, [M2X9]3- Fig 8.3 Dinuclear Metal Carbonyl , M2(CO)9
(M=Ru, Mo, W,
CO
(M=Ru, Mo, W,
O C
OC
C C
CO
OC
C
Metal-Metal bond OC Metal-Metal bond

OC
Metal ion Metal atom (M=Mn, Tc, Re)

The anion

The cobalt carbonyl Co2(CO)8 and the iron carbonyl , Fe2(CO)9 are also
dinuclear with structures similar to that of the manganese group carbonyls the
only difference being that in the cobalt carbonyl, two carbonyls are used for
bridging (i.e a carbonyl group is bonded to two metals) and in the iron carbonyl,
Fe2(CO)9 ,three carbonyl groups are bridging.
Trinuclear species. The rhenium(III) halides with the empirical formulae,
ReX3, (X=Cl, Br, I) have molecular formulae, Re3X9 (X=Cl,Br,I) and have the
general the structure shown in figure 8.4. When such halides are fused with alkali
metal halides , anionic species of the type, [Re3X12]3-,(X=Cl, Br) are obtained.
Tri-nuclear Metal clusters also occur between neutral metal atoms and

Fig 8.5 Structure of the Metal Carbonyl, M3(CO)12(M=Ru

Fig 8.4 Structure of the Trinuclear Rhenium Halides, Re3X9 Os)

CO
CO

CO
OC CO
OC CO

CO
C
O C CO
OC
O
=Metal Ion = Metal ato

=Halide Ion

Neutral molecules( see figure 8.5 above).

Tetranuclear metal clusters. Molybdenum, niobium and Tungsten form well –

established tetranuclear clusters . Thus, both molybdenum and tungsten form
tetranuclear clusters of the type, M4X8L4 ( M=Mo, W, X=Cl,Br; L=neutral ligand
such as a tertiary phosphine . An example of such a complex is shown in figure
8.6 Tetranuclear complexes are also known in metal carbonyls. Ir 4(CO)12 (Figure
8.7) is an example of such clusters.

Fig.8.6 Tetranuclear Complexes of the Type M 4X8L4

Fig.8.7 Tetranuclear Metal C
(M=Mo, W; X=Cl, Br, L=Tertiary Phosphine of the TypeM M4X12(M=Rh, I

L L
(M=Rh, Ir

L L

OCCURRENCE : Formation of Metal-Metal bonds is commonest in halides of

early d-block elements on 2nd and 3rd transition series . It is found that these
elements have relatively high enthalpies of atomization in comparison with the
other elements. It is for this reason that many halides of these elements in low
formal which appear simple are actually metal clusters. For example, when
MoCl2 is dissolved , only a third of the halogens is ionized.
 The Structure of the [M6X8]4+ metal Clusters
This cluster is common in the following

M [M6X8]4+ (M=, Mo,,W; ,X=Cl, Br,

= halide ion I)
M M=Metai ion
M
M Note a covalently bonded halogen at the
M centre of each face of the octahedron.

The Structure of the [M8X 12]6+ metal Clusters

This cluster is common in the following
M
n
[M6X12]
M = halide ion
+
M M =Metai ion M=, Zr2+, Zr3+, Hf2+, Hf3+ b3+, Hf3+ ; M=Nb2+, Nb3+,
M
M Ta2+, Ta3+, Mo3+, W3+

M
The halides are Cl, Br or I
is dissolved in water, only a third of the halogens are ionized.

,
Further Reading: FA Cotton and Ra Walton . Multiple Bonds between Metal
Atoms. Claredon Press. 2nd Ed.1993.

EXERCISE
1When CrCl3 is dissolved in water, it is 100% ionized. On the other hand, when
WCl3 is dissolved in water, only a third of the halides can be precipitated .
2. Iron is readily oxididized by chlorine even at room temperature. On the other
hand, tantalum must be heated to over 200 oC before any reaction statrts. Explain
3. Draw structures of complexes of the following metals which contain metal –
metal bonds :- (i) Manganese (ii) Cobalt (iii) Rhenium (iv Molybdenum (v)
Osmium (vi) Molybdenum