2n

o5S4t5
sgS acllot bns.HO
S g t oloeti
Teisiicho
9i1tot d nuit Compiexes
Niirosyl
adgneria
19dis
28231oritgsi
fon io Lsduloe 530
taio besouG3s
noano 9o ie)
US2UEa Todl 15-Organometallic
Chemistry

equriziois sie

gcG

41
43 42 hybridized be
group bent manner
Oxygen bonding
inthere(terminal cies As pressures,
sures replacementmixed Few
The
typically over Caulton, M.
Except monoxide), Syls nitric Unlike
NOlinear, in
stretching F.; species Since are Although
(7-C,H,)Re(CO),
are [Mn(CO)]++
NO* NOCI Co,(CO)%
2NOFe(CO),
+2NO +complexes
a or the [Co(CO).] oxide and
range Hillier, for the notatom. is isa
pairs diagnostic carbon carbonyl-nitrosyl
found K. a great the NO) case also
Cr(NO)4, and consistent
observed potential
temperaturesnitric
of G. NO by of
frequency
between I. bears
are avoidingbetweennitrosyl
However, = of known: the
about Coord. group similarity substitutingmonoxide, carbon
H.; known. 1672 the nitrosyl oxide containing
Vincent, no of
+
1000-2000 Chem. binary a with for donor, corresponding NO;
1500 of lone in a the cation, cm th e it in monoxide
the Cl-N=0, carbon
A large decomposes. complexes
and
in atoms in mode
NaBH, group + excess
nitrosyl Rev. M.metal ; pair. bent sp
one the nitrosyl which only
hybridization formal theNO, and 2C0, Fe(CO),(NO),
2Co(CO),(NO) ’3CO +
1900 cm Rosi,
1975, nitrosyl It monoxide.
nitrosyl importantnitrogenbehavior and v of generally ’ can
cmgroup is (bridging Mn(CO),NO can withnitrosyl
For 14, M. this coordination.43 iscarbonyl I(q'C,H)Re(CO),NOJ* +CO
+ chloride,
where positive lone
isoelectronic H,0 are
J. Manycause be nitric
carbonyl-nitrosyl 317-355. iscomplexes lone ligand
sensitive Chem. atom pairs
of occurs used known.41ligands
of
Although respect unfavorable
pair the the charge NO)
the compleves, nitrites, of + oxide:
Soc. nitrogen is coordinates on ’ the
in 2C0
to have that nitrogen,an both
tw o = as
Co(NO(CO), +
other Chem. the with For current excess They are
analogue mnost a
been causes on ligands. 1505 terminal
CI or
well
complexes,
bonding the +CO oxidation,
Commun. can nitrosyl atoms. CO,
cm. infrared nitrosonium may
obtained nitrosyl the
preferentially
a syntheses at characterized,
the be few product high
They it ligand, be
parameters considered of groupmoreAlthough is
the
nitrosyl distinctly cases
an of not stretching + formed
1986, in ligands 2HCO; temperatures
and
N-0 pure organicelectronegative each in salts:42avoid
behaves surprising bridging
438-439.form. group Eq. at
and (cf.
either have
stretch to appear the high readily but
is Guest, nitroso carbon frequen
15.38, (15.38) +
(15.37) (15.36)
found to be nitro CO (15.35) use (15.34)(15.33) many
in atom three that pres and
is be sp to a v of by

Og150
Chem. li
46 45 44Eisenberg, G.;
picometers. (b) Fig. CI orbitalsdonor poor
orbitalwhether
nitrogen both
found, the The derivativeofforms.when In regarded
thcount
e bent.
with, This

for isa
Commun.
125-126.
Hodgson,
Pierpont,

1983, P.;
D. (RuPPh)-(NO),CI]".
M.
Ibers, 15.15 234.3 system),46
with
onavailableatomquestion the
Thelinear
including
apical
product
Ir(Ph,P),(CO)CI The
first
linear
oxidation
10724
the unpaired
:N=0:
M+
for In
relative
example, J.
R.Complexes 240.0 position the asthe
Tew, C. D. [StructureA. concomitant the and and
G.; J.; Inorg. Ir
pair well-characterized
iscomplex:
Vaska's antibonding linear neutral a
J. metal three-electron
D.Ibers, (a) the (bent state
term. Eisenberg, Am. 18
to of of bent the square a
those G.; Chem. it.
pair electrons (Fig. coordinated case
J. (a)
Chem. containing are group) If whether remarkable
nitrosyl pyramidal method, atom
All
Larkworthy, +
metals
in in A. fromPhenyl canthere 15.15a),44 NO includes
fluoride 1972, already electron
R.
Inorg. method
Inorg.
Soc.
Hodgson, donor
backreside are orgroups45
nitrosylin a
carbonyl-nitrosyl 11, groups bent whether
question
BF, »example NOthe
complexes. Chem. 1968, filled available example with ligand
M=N=Ù
M-N=Î: th
L.
Chem. 1088-1094. bonding. there Other ine and of
nitrosyl
háve NO:
F.: 90, D. (an a when nonbonding
Sandell, 1968, ligand (Fig. bent is electron a
1972, 4486- J.; been and
[Ru(Ph,P),(NO),CI"(PF,). of bent
electron-rich nonbonding there wil complexes a
viewed
7, Payne, groups: On 15.1 nitrosyl bent;
Reproduced
2345-2352.
allow be bent
systems B.; I1, 4488. omitted is wil nitrosyl
the forced counting,
1088-1094. a be5b). nitrosyl it as electron
Povey, Structure
from(b) N. (a) the
low-lying
236.5 other linear ligand
with is a
are (Ir(PPhs)(CO)XNO)CI]" C.; for coordinateda
with system),nitrogen MOs to two-electron
as Complexes
Nitrosyl
relatively McGinnety, clarity; a ligand pair a a
D.See hand,
C.; permission.J (b)
onreside or bent (2 one-electronlinear
Mason, also
metal-based the bent Ir-N-0 on
compared
electron
rich distances e if to
thfunction in M-NO was nitrosyl
Bell, all metal resolves an
nitrogennitrosyl
Pierpont,G.
C. J. pair which that donor
J. A.; the
J. L. of (an orbital donor.
Chem. K.; Pearson, are as
molecular have = found ion, as
inand electrons
low-lying electron itselfcontains
an on 124°)(15.40) in (15.39) & well ligand
Mingos. been NO*.
both
Soc. sp the into in The 651
R. o at a as is
 15-Organometallic
Chemistry

47 ligands. t15.16
he Fig.
1981. J.
Enemnark,
Topics M=C=0
MC=O hybridization
Linear,
2 sp accepting from
nitrogen factfrom ion ligand) (a between
structure conclude
(Ru(PPh),(NO),CI]" lengths data withessentially ever,N-0 bonding
H.; M=N=0
-N=O three-electron systemhybridization of COmust
Feltham, what (a We nitrosyl
in being a The is
Inorganic two-electron (Fig. difficult.
systematic the
J. Geometry
atom molecular can tw o in bond shown occupy
a
happens in that insensitivity (athere
s
metal-nitrogen
H.; pair a NO, ligands
R. and three-electron 15.17). actually the and o-only in
Feltham, O=cEO the of
and D. o=N=0 of ametal is anda
in an
Coord. parallel
(linearvs. electrons
orbital donor), complex three. NO, Withinerrors Fig.
and donor) The NO metal-nitrogen bent a essentially
(Fig.
Organometallic R. see carbonyls). short bent
bond
experimental
and are of
nitrosyl 15.16.
Chem. D. correlations "stereochemical 18-electron of as the inthe 15.bondsystem.
J. bent) largely wouldindeed io n NO the metal-nitrogen 15b)
becomes to process order, the NO
Rev. Am. H [Co(diars),NO]*
a same nonbonding
of are
crystallographic would The lengths are
tereochemistry; Chem. one-electron metal violate it bond A
1974, nitrosyl
for for bond in
comparison
is. rule of 106,
length
available.
13, Soc. analogous character Reactionpredicts electron both
error, length be bent accord in
-M-C hybridization
Bent,sp² control the 115, the
339-406. ligands longer(185.9
system, bond orbital
1974, the and(117.0 the ruthenium
with
(b) donor,18-electron to
Geoffroy, H H (where
96,
compounds
correlated
with of to of bent
small than pm). (173.8 of
Feltham, this
that pair apical 120 analysis
and in the th e on
valence'" an contrast,
5002-5004, a the shift pm, changes that It complex view bonding the
G. coordination orbitalcomplex rulenitrosyldiars and 116.2 and would pm)
L., R. containing with
respectively. make of just nitrogen,
basal linear indicating
Ed.; results.47 unless on pm). in ashows presented. possibilities
5004-5005.
D.; hybridizationthe of
is a
linear becontaining
Enemark,
withgroupresultant a evaluation bond
Wiley: nitrogen. bidentate arrangements, expected
a TheN-0 a requiring
carbonyl site pair th e nitrosyl. relatively
As wil We order
NewEnemark,
capable thiocyanate N-0 substantial In
J. NO This is change
be for
York, H. diarsine can bonds coupled of that the both
In
shifted linear trigonal
NO
goes is lie s only bond such How. long, lineartypes
of in in the and
of
 Dinitrogen Complexes 653

170 135
185

Co
168 26

J2535
9290 232 SCN 334
236
233 As 210
234\878s
99

236 119
As
AS
161

Fig. 15.17 Stereochemical control of valence. Note localization of the lone pair on the
nitrogen atom and bending of the nitrosyl group upon addition of thiocyanate ion to the
153ets
i i AvCoordination sphere. Bond lengths are in picometers. [From Enemark, J. H.; Feltham, R. D.
icidrssoTiniba0Proc. Natl. Acad. Sci. USA 1972, 69, 3534. Used with permission.J

Dinitrogenh Molecular nitrogen, N,, is isoelectronic with both carbon monoxide and the nitrosyl
9 gion but,despite the numerous complexes of CO and NO, for many years it proved to
Complexes48 se_ be impossible to form complexes of dinitrogen. This difference in behavior was
becdiR i aii tusually ascribed to the lack of polarity of N, and a resultant inability to behave as a
szno gabics titThe first dinitrogen complex,characterized in 1965, resulted from the reduction of
eidt oisaaibtc Boru.commercial ruthenium trichloride (containing some Ru(IV)] by
a012.lans 7oSThe pentaammine(dinitrogen)ruthenium([I) cation that formed could hydrazine hydrate.
be isolated ina
b8s 2221 JE baa D- variety of salts, 50 Soon other methods were found to synthesize the complex, such as
the decomposition of the pentaammineazido complex,
7siGon tinb bdirect reaction with nitrogen gas: (Ru(NH),N,],and even
ei sri no fetq Zn(Hg)
(Ru(NH),CI]t H,0 (Ru(NH,),H,0)+ (15.41)
6 e dey 0c. IRu(NH);H,OJ* + N, [Ru(NH,),N,]'* (15.42)

48 Kaul, B. B.; Hayes, R. K.;

George, T. A. J.
H.; Huttner, G.; Zsolnai, L. Chem. Ber. Am. Chem. Soc. 1990, I12, 2002-2003. Birk, R.; Berke,
Pickett, C. J. Adv. Inorg. Chem. Radiochem. 1988, 121, 1557-1564. Henderson, R. A.;
Leigh, G. J.;
Chem. Rev. 1984, 55, 55-112. Leigh, G-J. Acc.1983, 27, 197-292, Pelikán, P., Boa, R. Coord.
Hutchison, J. E.; Lopez, M. A.; Guilard, R. J. AmChem.
Chem.
Res. 1992, 25, 177-181. Collman, J. P.;
Note, however, that thedipole moment of Soc. 1992, I14, 8066-8073.
(0.112 D). carbon monoxide is extremely small: 0.375 x 10Cm
2.tetst es42)Allen,
50
A. D.; Senott, C. V. J. Chem. Soc.
Chem. Commun. 1965, 621-622.
 25-36. 181, 1979, Chem.Organomet. Riley,
P. F.; M.pert, 16JaneS, Me,|
Lap [CH(SiMes)a\(N).
Jeffery,
J.; (n-C,H),Zr coordination
in of
mode J.supports
thatI.adwevidence
oscopic good fairlyanalysis, X-ray verified
bystructures side-on no
been have thereAlthough s4
4872-4873. 2R ee
110. 1988, Soc. Chem. Am. T.J. Higuchi, T.; Ueda, Kaminaka,
M., T.Adachi,
; Yoshida,,
T.; 53
1289-1293. 24, 1968, Crystallogr.
Sect. S S
B Acta Nyburg,
C. S. Bottomley,
F., s2
589-625. 78, 1978, Rev. Chem. Richards,
L. R. R.Dilworth,
; J. J.;Chatt, S1
cisCr(CO),N,
and complexes.
Both dinitrogen carbonyl instability
of the for
ccounts also COability
ofaccepting superiorT Theorbital. metal the with overlap
favors which 5.20), Fig. (see atom carbon concentrated
the on orbitalis
antibonding N
the that fact the and 5.18) Fig. (see molecule COthe exists
in polarity whatever of 110.5
basis thexpected
e on beto Thiacceptor.
iss betterm alsao but donor bettero onlay N
176°
nmonoxide
ot is Carboncomplexes. dinitrogen the weaker
insomewhat butsimilar 200.8.s
complexes
are dinitrogen carbonyl
and bonds
in
metal-ligand the thappears
at It
orti ush trans-Mo(N),Me,[
16]aneS for cm 1890 Mo
and [Ru(NH),(N,)JCL,
1955 atand for cm2105 appear
at bandsstretching N-N stes/
strongexample, frequency.
For lower shifts
ato and active infrared becomesnnvibration 199.1S
ordination,
this Upon cm. 2331 isN,freefrequency
of stretching Raman The Yu Seib
complexess4 nonbridging confirmed in been have N,binding by side-on exämples of botlue fi (N) 177°
NoNS). in2.5 orderof bond faor pm 111.6 of
value the nitrogen
(cf. orbitals
of 110.8
onding tT
he into density electron donation
of the from bond gen-nitrogen
triple Sts dani N)
nitro theweakening
of suggesteda pm), (109.8 nitrogen molecular found
in 9nioil
that ni
thangreater slightly ispm) (110.7 length bond N-N mean complexes.
The ammine 1E 0 permission.]
bond
inMo--NH, the to than bond Mo-CO anlength
to similar
in withriwhich
more is 4872-4873.
Used 110,
bond, Mo-N short the fromapparent orbitals
isantibonding iT
nto metal the from 1988, Soc. Chem. Am. J.
density electron donation
of Back metals. bonding
to its resembles
inCO greatly N, Higuchi,
T. T.; Ueda, M.;
thatshow and typical complex
are this foresults
r The15.18.5$ Fig. shown
in complex Kaminaka, Adachi,
T.; T.;
ioether bis(dinitrogen)
crown including
the determined, been complexes
have trogen Yoshida, [From
picometers.
dini other structures
of many then, Since lengths. bond
determination
of accurate in
lengths
are Bond
16]aneS.)(N2)2 Mo(Meal
vented crystal the disorder
in but on, end waslinkageRuNN the nature
of of 15.18 Fig.
the indicated
that complex52
ruthenium-dinitrogen original the study
of X-ray An Structure
bridging side-on terminal side-on
M N
M
N N
bridging end-on terminal end-on
M-NN-M M-NN
cases:51 bridged
for two andligandsdinitrogen terminal possibilities
for structural two areThere
(1543) [Ru(NH,),N,Ru(NH,),]4*
H,0 +
H,0]²[Ru(NHJ),
t N,J[Ru(NH,),
*+
complex: bridged formation
aof theexhibited
in aiso 15.42is Eq. water
in
lacementof its shown
by dinitrogen nucleophilicity
of strong
unexpectedly The
Chemistry
15-Organometallie 654
 NH3 toconversion
Nz of photolytic afor Chapter13 2909-2912.
See Z7, 1983,
Chem. Inorg. Tisdale,
C. R. A.; George,
T. 23-28, 17. 1984. Res. Chem, Acc. Colquhoun,
M. H.
6877-6879. S8
110, 1988, Soc. Chem. Am, W.J. J.
Ziller, A.; Ulibarri,
T. J.; Evans,
W.
2294-2301. S7
108, 1986, Soc. Chem. Am, J.
R.R. Ryan, J.; Kubas, G. Wasserman,
J.; H.
3645-3651. 108, 1986, Soc. Chem. 0
Am. J.Turner,
J.J. Poliakoff,
M.; K.; Upmacis,
R. S5
many view
for prevailing the1907),synthesized
in [Me,Ptll, (e.g., present arbonds
e
single M-C which complexes
in examples
of early some are thereAlthough
M=CR M=CR2 M-CR3 Complexes Alkyl
recently: more
beto understood
much Carbides
come have bonds triple anddouble, single,
metal-carbon containing compounds
Transition century. 19th the to back compounds)
dates organomercury andreagentsmetal Carbynes,
and
Grignard compounds
(e.g., group main bonds
in metal-carbon Carbenes,
chemistry.
The organic position
in
central occupieda singlelong have oxygen chemistry
nitrogen,
and of
carbon, nonmetals
assuch and carbon betwecn bonds triple anddouble, Single,
Alkyls, Metal
19).Chapter (see
involved systems enzyme the nitrogen
and of
fixationbiological process
of related closely the intinsight
o provides alsochemist.58
It
thchallenge
e to long-standing atmosphere,a the from nitrogen fixation
of direct
possibilities
of up
opens nitrogen, of
state
electronic thalteration
e of considerable
with thoseespecially dinitrogen, containing complexes synthesize ability
to The
dinitrogen. free found
in that than shorter even ispm) (108.8 distance bond N-N
enough
the strangely but bond, N-N reduced implyinga Sm(II), presenceof the
suggest distances bond Sm-N arrangement.
The planar ainare atoms nitrogen two
the and atomssamarium two the Sm(C,Me,),
N,, and reaction
of the fromobtained
complex, samarium this 15.19),57
In (Fig.
felement complex
an of dinitrogen first the
also exampleis reported recently however,
anad known, also complexes
are side-on
Bridging example. fo15.43,
r Eq.complex
of
diruthenium the incase the isnation;
this
coordi end-on exhibits usually ligand,
it bridging functions
aas dinitrogen When
(15.44)
Mo(CO),(PCys),
N, Mo(CO),(PCys)a
N, +
temperature.56 room isolated
at
becan (PCy,),
N, Mo(CO), hence, stability; enhance
significantly density
to electron
suficient provide phosphines
can carbonyls
with the of
someReplacing warmed.55
when
decompose temperatures,
but loinvestigated
w at been Cr(CO),N,),
have
permission.] Sm:
with 6877-6879.
Used Sm
110, 1988, Soc. Chem.
Am. J. W.
Ziller,
J. À.; T.
Ulibarri, J.; Evans,
W.
Sm('-C,Mes),(N,).
[From
Structureof 15.19 Fig.
655 Carbides Carbynes,
and Carbenes, Alkyls, Metal