8 Metal Carbonyls

BY B. J. BRISDON

1 In t roduc t ion

The format o f t h i s repor t has been changed s l i g h t l y from t h a t used l a s t year, both i n order t o accommodate f u r t h e r space l im i ta t ions , and simultaneously t o recognise recent developments i n metal carbonyl chemistry. As previously, emphasis has been placed on synthetic, s t r u c t u r a l and general chemical aspects o f d iscrete metal carbonyl e n t i t i e s a t the expense o f t h e i r surface immobilised and c a t a l y t i c chemistry.

Two major reviews concerning gas-phase metal carbonyl species have been published i n 1987.132 I n the former, gas-phase t r a n s i t i o n metal negative ion chemistry has been surveyed and much quant i ta t i ve data and qua1 i t a t i v e react ion chemistry presented on a wide range o f metal carbonyl fragments.’ I n the la t te r , studies o f coord inat ive ly unsaturated carbonyl der iva t ives using t rans ien t i n f r a - red spectroscopy are highl ighted.2 reviews on theore t ica l ca lcu la t ions o f e lect ronegat iv i ty values , 3 and on the Fe( CO), i n t e r ~ n e d i a t e . ~ t r a n s i t i o n metal complexes includes reference t o metal c a r b o n y l ~ , ~ and reviews devoted t o anionic t r a n s i t i o n metal hydrides,6 and the reactions o f Ru c l u s t e r carbonyls under m i l d condi t ions7 have been published. A comprehensive a r t i c l e on b u t t e r f l y c l u s t e r complexes o f the Group 8 t r a n s i t i o n metals i s contained i n *ogress in Inorganic @emistryre and a t ime ly review on theore t ica l models of c l u s t e r bonding addresses the analogy between h igh nuc lear i t y c lus te rs and bulk metals.9

Metal carbonyl fragments a lso feature i n

An a r t i c l e on the photoelectron spectroscopy o f organo-

2 General and Theoretical StudSes

A general procedure f o r the reduct ive coupling o f the two CO l igands i n [M(C0)2(dmpe)2C1] (M = Nb, Ta) has been reported and the molecular s t ructures o f four of the r e s u l t i n g b i s ( t r imethy ls i 1oxy)ethyne conta in ing products determined.1° Rapid revers ib le add i t ion o f two GO groups t o a t r i n u c l e a r P t c l u s t e r wi thout c lus te r breakdown has been observed.” detected i n the [0( Ph)C2B10H10]- anion, which consis ts o f a nido-shaped [PhCBloHlo]’ residue capped w i t h a CO l igand, whose C-0 separation and pos i t ion r e l a t i v e t o the cage C atom on the open carborane face, are r e a d i l y r a t i o n a l i s e d by f r o n t i e r o r b i t a l considerations.12 The generation o f f ree o r l i g a t e d CO from CO:! has received fur ther a t t e n t i ~ n . ’ ~ ’ ~ ~ An unprecedented i n s e r t i o n o f a metal

A pentuply-bridging CO group has been

[For references see p . 141

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noi-iy i n t o one C-0 bond o f C02 y i e l d s a complex containing both terminal 0x0 and carbony1 l igands on a mononuclear metal centre,14 whereas in te rac t ion o f C02 w i th [M(C0),J2- (M = C r y Mo, W ) causes reduct ive d ispropor t ionat ion w i th the formation o f M(C0)6 and [C03j2-, probably via the intermediacy of an d - C O 2 c0mp1ex.l~ Electrochemical reduction o f CO t o hydrocarbons a t various metal electrodes i n aqueous so lu t ion has been explored,16 and several studies published on the reductive hydrogenation o f coordinated CO leading t o the formation of f ~ r m y l , ~ ~ , ~ * o r oxymethyl species. l9 the reduct ive cleavage of CO t o C2+ and 02- on surfaces has a lso appeared.20

Further repor ts on molecular compounds used f o r modelling

The synthesis and spectroscopic character isat ion o f the f i r s t b inary zirconium carbonyl complex has been described by E l l i s and coworkers.21 metal naphthalenide reduct ion o f ZrC14.2THF i n the presence o f CO and a crown- ether gives s a l t s o f the [Zr(C0),l2- anion i n 25-35% y i e l d . products are s tab le a t room temperature under an argon atmosphere. accounts o f the formation o f the novel hafnium carbonyl der ivat ives [Hf(arene)2- (CO)]22 and f H f ( n5-C5Mes) ( COf2( d m ~ e ) C l ] ~ ~ have a1 so been pub1 ished.

A l k a l i -

The a i r -sens i t i ve Prel iminary

Fol lowing the recent i s o l a t i o n o f the f i r s t stable, molecular ac t in ide carbonyl complex, the e lec t ron ic s t ruc tu re of Cp3UCO and re la ted species have been invest igated by X,-SW molecular o r b i t a l ca lcu lat ions i n which theore t ica l corroboration fo r extensive U 5f -+ 2~-back bonding i s presented.24 Molecular o r b i t a l ca lcu lat ions based on density funct ion theory have been car r ied out on the i n t r i n s i c mean bond energies and f i r s t CO d issoc ia t ion energies of several binary metal carbonyls. A deta i led discussion o f those e f f e c t s which determine the M-CO bond strengths f o r corresponding 3d , 4d and 5d analogues i s included.25 Other theore t ica l studies per t inent t o metal carbonyl ,26 -carbony1 hydrideZ7 and -carbonylate anions28 have a lso been reported. concerned w i t h the e lec t ron ic s t ructures o f metal atom c lus te rs were published i n 1987. Harmonic Theory have been appl ied t o deltahedral and the same authors have extended t h i s theory t o include capped and r a f t c lusters .30 Analyses o f the e lec t ron ic s t ruc tu re o f Mn (n = 3-6) c lus te rs31 and MqE232 (M = t r a n s i t i o n metal; E = main group atom o r canonical fragment) organometallics have a lso been given.

Several notable contr ibut ions

Thus Group Theory and pr inc ip les inherent i n Stone's Tensor Surface

3 Chemistry o f Metal Carbonyls

3.1 Mononuclear Carbony1s.-The 13C0 enrichment o f a large range o f mono-, b i - and t r i -nuc lear metal carbonyls a t 25 "C and pressures up t o 1 atmosphere o f 13C0 have been examined using KH and NaBH,, as exchange promoters.33 With the ex- ception of R u ~ ( C O ) ~ ~ , NaFIH4 i s equal ly o r more e f f e c t i v e than KH, and i s therefore preferred i n view of i t s ease of handling. Time resolved i n f r a r e d studies o f gas phase V(CO), (n = 5-3, and poss ib ly 2) have been car r ied out and r a t e constant data evaluated.34 Some assianments are a t variance w i t h c e r t a i n r e s u l t s from

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8: Metal Curbonyls 137

zi:?ix i s o l a t i o n studies. w i th 02,35 and reactions o f the rad ica l anion [Cr(CO),]y w i t h a ser ies o f alkenes and p o l y e n e ~ ~ ~ have been examined, and evidence presented t h a t C r atoms are formed by both d i r e c t and sequential d issoc ia t ion processes i n the mult iple-photon d is - soc iat ion o f C ~ ( C O ) G . ~ ~ (M = C r , Mo, W ) w i t h Me3NO i n the presence and absence o f PPh3 have been ex- plored. 38 Relat ive p a r t i a l photo ion izat ion cross-sections have been measured over the photon range 16-115 eV f o r the valence bands o f f ree CO and M(C0)6 (M = Cr, Mo, W), and the data compared w i th resul ts . f rom theore t ica l calculat ions.39 K ine t ic studies have been performed on competit ive C-H and O-H ox idat ive add i t ion reactions o f the 14e [Mn(CO)3]' anion,4o and on the e lec t ron t rans fer react ions o f Re(CO)5 radicals.41 Radical intermediates have a lso been i d e n t i f i e d i n the formation o f Fe(CO)5 from Fe3(CO)12 and CO.

of F e ( c 0 ) ~ , ~ ~ as wel l as photochemical react ions o f the c a r b ~ n y l ~ ~ and i t s derivative^^^,'+^ under various condit ions have been described.

The ion-molecule reactions o f the [Cr(CO),]- anion

The k i n e t i c s and mechanism o f the reactions o f M(C0)6

The mult iphoton ion isa t ion spectra

3.2 Binuclear Carbony1s.-The h igh ly se lect ive coupling o f anionic carbonylman- ganate( - I ) and carbonylmanganese( I ) cations noted e a r l i e r i n electrochemical redox studies has been examined i n more d e t a i l , and the mechanism of Mn-Mn bond formation by ion-pa i r a n n i h i l a t i o n determined. o f Mn2(CO)lo has been studied us ing laser photo lys is i n conjunction w i t h e lect ron impact ion isa t ion and mass spectrometric determination o f primary photofragments. Exc i ta t ion o f the O* s ta te o f the carbonyl leads t o both bond homolysis and l igand loss, whereas e x c i t a t i o n o f the T* s ta te leads t o j u s t l igand Photolysis o f samples of MnRe(C0)Io enriched s p e c i f i c a l l y w i t h 13C0 on the Re end y i e l d s [Mn(CO)4(~-CO)Re(CO)4] fo l low ing expulsion o f CO from the Mn end of the dimer.49 y i e l d s [Re2(CO)g(N2)] conta in ing N2 i n an equator ia l s i t e . were obtained f o r Mn2(CO)lo and MnRe(CO)lo.5u N.m.r. methods have been used t o invest igate the exchange o f f ree CO i n so lu t ion w i t h c02(co)8, and t o determine rates o f CO d issoc ia t ion and hence a c t i v a t i o n parameters. 51 The d ispropor t ion- a t ion o f CO*(CO)~ induced by pyr id ine i s i n h i b i t e d by CO, and a rad ica l mechanism wi th p a r t i a l chain character i s proposed t o account f o r the react ion orders.52 However, i n hydrocarbon so lu t ion i n the presence o f a moderate amount 0.f pyridine, homonuclear ion p a i r i n g from CO,(CO)~ occurs t o y i e l d [ C o ~ y ~ t C o ~ ( C 0 ) 1 ~ ) ~ ] , which contains two [Co3(C0),o]- u n i t s coordinated via CO O-atoms t o a planar [Copy4] +

un i t .53 I n an i n t e r e s t i n g extension of previous biochemical l a b e l l i n g techniques described i n l a s t year 's S.P.R. on Organometallic Chemistry, b inuc lear metal carbonyl species inc lud ing C02(C0)8 have been used as improved i n f r a r e d b io - l o g i c a l markers f o r the in v i t ro detect ion o f femtamole concentrat ions of est ra- d i o l receptor s i t e s i n lamb u ter ine cytosol.54

Gas phase photodissociat ion

The photosubst i tu t ion o f Re2(CO)lo i n l i q u i d xenon doped w i t h N2 Simi la r r e s u l t s D

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138 Organometallic Chemistry

3.3 Polynuclear Carbony1s.-Preliminary r e s u l t s f o r laser- ion beam photodis- soc iat ion studies o f i o n i c c l u s t e r fragments o f t r a n s i t i o n metal carbonyls have been presented. formed by electron-impact i o n i s a t i o n o f Mn, Fe and Co carbonyls have been measured, as we l l as upper l i m i t s t o bond d issoc ia t ion energies f o r M-M and M-C0.55 pr imar i l y on a l l - te rmina l carbonyl coord inat ion i n l i g h t petroleum solut ion, but i n a frozen CH2C12 so lu t ion the br idg ing l igand s i t e s are subs tan t ia l l y populated.56 Photosubsti tut ion and photofragmentation i n Fe3(C0)12 and and the redox chemistr ies o f Ru3(C0)12 and O S ~ ( C O ) ~ ~ ~ ~ have been explored. The spectral detection, character isat ion and r e a c t i v i t y o f coord inat ive ly unsaturated O s g -

(CO)ll, produced from Os3(COf12, has a lso been recorded.59 A f u l l repor t on the preparation and s t ruc tu re o f 0s4(C0)15 has been published.60 On react ion w i t h COY i t a f fo rds O S , + ( C O ) ~ ~ , which has a puckered OSL, framework and i s a metal carbonyl analogue o f cyclobutane.61 coupling t o natura l abundance 1870~ have been observed i n the 1 3 C and 31P n.m.r. spectra o f osmium carbonyl c l u s t e r complexes, and t h e i r study y i e l d s a new i n - s igh t i n t o the f l u x i o n a l behaviour of these polynuclear compounds.62 measurements show t h a t spontaneously paramagnetic c lus te rs composed o f between 10-40 osmium atoms a l l have magnetic proper t ies reminiscent o f molecules, ra ther than bulk metals.63 c lus te rs have been discussed,64 and the synthesis and s t ruc tu re o f the [ I r 1 2 ( ~ -

co)8(co)l8] anion formed by ox idat ion o f [ I r ~ ( C 0 ) 1 5 ] ~ ' has been reported. The 162 valence e lect ron Ir12 core s t ruc tu re may be represented by superimposition o f three face-sharing octahedral uni ts.65 quadrupole mass spectrometry, on treatment w i t h CO y i e l d an ion ic species [Nin(CO)m]+ and [NinC(CO)l]+ (n = 1-13), w i t h values o f m and 1 which cor re la te extremely we l l w i t h Lauher's electron-counting ru les.66

Relat ive photodissociat ion cross-sections f o r [Mx(CO)y]+ ions,

An EXAFS study o f Feg(C0)12 i n s o l u t i o n has shown a s t ruc tu re based

Low i n t e n s i t y sate1 li tes r e s u l t i n g from

E.s.r.

Factors causing M-M bond shortening i n some Ir carbonyl

Nickel c l u s t e r ions, s ize selected by

It has been shown t h a t CO d issoc ia t ion i s the r a t e determining step i n the subs t i tu t ion react ions of the heterometa l l ic carbonyls Fe2Ru(CO)12 and FeRu2- ( C 0 ) 1 4 , ~ ~ and the Fe s i t e symmetries i n a ser ies o f Fe-containing M5 and M6 metal carbonylates have been i n f e r r e d from Mossbauer studies.68 The synthesis of [PPN][RuRh5(CO)16] has been reported and i t s s t ruc tu re shown t o be isomorphous w i th [PPN][FeRh5(C0)16],69 and i n a pre l iminary communication the revers ib le formation o f two t r i a n g u l a r metal c lus te rs from the puckered r a f t core o f Os4PtZ- (CO)18 fo l low ing treatment w i th CO has been described.70

3.4 Carbonyls conta in ing Main Group Metals.-There has been considerable recent progress i n the f i e l d o f heteronuclear metal carbonyls containing both t r a n s i t i o n metals and main group elements. Si2Co6(C0),,, shown by X-ray analys is t o contain a novel pseuodo-octahedral trans-Si2C04 core, w i t h S i i n a d is to r ted square pyramidal c o n f i g ~ r a t i o n . ~ ~

Reaction o f S i 2 H 6 w i t h Co2(C0)8 y i e l d s

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8: Metal Carbonyls 139

deta i led paper on the redox chemistry of Ge, Sn and Pb conta in ing i r o n carbonyl c lus te rs has a lso been published, i n which the s t ructures o f [GeFeb(C0)14]2' and [Pb(Fe2(C0)812] are reported. 72 Oxidation of the product o f the react ion between [Fe2(CO)a]2- and SbC13 produces [ {Fe2(CO)8(~4-Sb)}2(Fe2(co)6} ] i n which Sb bridges Fe2(CO)6 and Fe2(CO)a groups.73 The f i r s t example o f a Mn-Bi s ing le bond i s claimed i n [BiIMn(C0)513]. This molecule e x h i b i t s pyramidal geometry about B i , and re l ieves possible s t e r i c in te rac t ions between Mn(C0)5 moieties through cont- r o t a t i o n about Mn-Bi vectors. 74

containing 1, 2 and 4 B i atoms are reported t o be formed s t a r t i n g from BiC13 and [BiiFe(C0)41J3'.75 Further examples o f Bi-Co carbonyl c l u s t e r compounds have been characterised c rys ta l lograph ica l l y by two independent groups o f worker^.^^,^^ Reaction o f NaBi03 w i t h M3(CO)12 (M = Os, Ru) i n MeOH affords the new mixed carbonyl c l u s t e r der iva t ives [M4(C0)12(p4-Bi)2] as wel l as [M3(p-H)3(CO),(~~-Bi)] .78

3.5 Carbonyls containing Non-metals.-Vibrational studies on carbido carbonyl c lusters containing M5C (M = Ru, O S ) , ~ ~ Re6C and N i a C cores80 have been described, and the c rys ta l s t ruc tu re o f the [Re7C(CO)22]- anion determined.81 the b u t t e r f l y carbido c l u s t e r complex [PPN]2[Fe4C(C0)12] w i t h a v a r i e t y o f a1 ky la t ing agents have been explored,82 and the synthesis o f several heterometal l ic carbido c lus te rs conta in ing three Fe atoms reported.83 [ P P ~ I + ] [ F ~ ~ R ~ C ( C O ) ~ ~ ] under hydroformylat ion condi t ions has been examined, and the synthesis and s t ruc tu re o f [PPh4][Fe3Rh3C(CO)15] described i n the course o f t h i s study.84 Three electrochemical and spectroscopic studies have been c a r r i e d ou t on carbido carbonyl c lus te rs containing ten and eleven 0s atom^.^^"^^ of f i v e ox idat ion s tates were characterised dur ing an electrochemical study on [Os loC(C0)21+]~- .~~ Using v ib ra t iona l parameters obtained from so l id -s ta te X-ray d i f f rac t ion data fo r [PPh&[Rh6C(C0)13], i t has been possible t o show t h a t there i s extensive corre la ted v ib ra t iona l motion o f the seven CO l igands around the Rhh equator ia l plane o f the anion. This so l id -s ta te behaviour i s i n accord w i t h the lowest energy CO migrat ion pathway found by previous n.m.r. studies i n so lut ion. This method o f fe rs a powerful l i n k between thermal motion i n the so l id -s ta te and dynamic rearrangements i n so lut ion.a8 [ C O ~ N ~ ~ ~ C ( C O ) ~ ~ ] ~ - and [Co3Ni9C(C0)2012' have been shown t o be isos t ruc tura l , w i t h the metal core formal ly derived by d i s t o r t i o n o f a tetra-capped t r iangu la ted d o d e ~ a h e d r o n . ~ ~ I n a b r i e f repor t on gold der ivat ives of n i t r i d o c lusters , the s t ructure and 15N n.m.r. spectrum o f [ P ~ ~ P A U F ~ R U ~ N ( C O ) ~ ~ ] have been repor ted and compared w i t h data on [ H F ~ R U ~ N ( C O ) , ~ ] . ~ ~ A new example o f a 14-0x0 l igand con- t a i n i n g metal carbonyl c l u s t e r has been iso la ted from the react ion o f [PPNI2-

[Fe3(u3-O)(CO),] w i t h [Mn(C0)3(NCMe)3]PF6, pos i t ion i n the b u t t e r f l y metal frame a r r a n g e ~ n t . ~ ~ (CO)9 have been prepared from the react ion o f [Fe3H(CO),,]- w i t h S8,92 and some photochemical l y i n i t i a ted reac t ions o f [ FeS( CO), 32 exami ned.93 Th [ Fe2S2 (CO) 6 i 2 '

Another ser ies o f an ion ic i r o n carbonyl species

Reactions o f

The transformation o f

A t o t a l

The new b i m e t a l l i c carbido c l u s t e r anions

The Mn atom occupies a wing t i p Both [FeS(C0)3I2 and Fe3S2-

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140 Organometallic Chemistry

has beirn used as a c l u s t e r precursor i n the formation o f [ M O F ~ ~ S ~ ( C O ) ~ ] ~ - , which can be ox ida t ive ly decarbonylated t o a persul phide bridged MoFe3S4 double cubane d e r i ~ a t i v e . ~ " (E = S, Se, NPh, PPh), undergo rap id e lect ron t rans fer chain ca ta lys is (ETC) of l igand subst i tu t ion. s t rongly modulated by the nature o f the br idg ing ~ a p ( E ) . ~ ~ c lus te r carbonyls conta in ing y4-S bridges have been reported. 96,97

[ R u ~ ( P ~ - S ) ( ~ ~ - C O ) ( C O ) ~ ] w i t h Ru3(C0)12 and water gives low y i e l d s of [Ru~(P-OH)~- (y4-S) (p-C0)2( CO) 1 6 1 which e x h i b i t s in t ramolecular H-bonding. 97 The s tab i 1 i sat ion o f y-Se22t and n3-TeZt l igands has been achieved, and the s t ructures o f [M(n3-Te3)- (C0)4][SbF6]2 (M = Mo, W ) and [Few(Se2)(Co)8][SbF,]2 d e t e r ~ n i n e d . ~ ~ , ~ ~

A ser ies o f i sos t ruc tura l t r i - i r o n c lus te rs [Fe3(~3-E)2(CO)g]

The rate, e f f i c i e n c y and s e l e c t i v i t y of ETC cata lys is are

Reaction o f A ser ies o f Ru

4 Metal Carbonyl Hydrides and Halides

Further invest igat ions i n t o the re la t ionsh ip between carbonyl hydrides and d i hydrogen complexes o f metal carbonyl moiet ies have been car r ied out. l o o

Photolysis o f Group 6 metal carbonyl alkene complexes i n l i q u i f i e d noble gases doped w i t h D2 leads t o very l a b i l e complexes i n which an alkene and D2 are co- ordinated t o the same metal centre.lol dianion and i t s protonated product [Re2H2(y-H)(C0),]- have been described,lo2 and a novel tetrarhenium unsaturated anion [ R ~ I + ( ~ - H ) ( ~ ~ - H ) ~ ( C O ) ~ ~ ] - has been i d e n t i f i e d . l o 3 appears t o be delocal ised on two shor t edges o f the d i s t o r t e d te t rahedra l Re4 core. The s t ructure o f [H2NPr2][Fe3H(C0)11] has been determined i n order t o invest igate CO---H bonds ,lo4 and 'H n.m.r. s p i n - l a t t i c e re laxa t ion studies per- formed on hydridometal carbonyl c lus te rs o f Ru and Os.lo5 exchange w i t h l2C0 i n [M3H(CO),1]- and [M3D(CO),l]- (M = Ru, 0s) have been examined, i n order t o provide fu r ther i n s i g h t i n t o the nature of the ca ta lys is o f the water-gas s h i f t react ion, and reveal a basis f o r the apparent d i f ferences i n a c t i v i t y between these Ru and 0s analogues.lo6 formation of [ R U ~ H ( C O ) ~ ~ ] - by hydrogenation o f [Ru3(CO)11(C02Me)]- have provided an i n s i g h t i n t o mechanistic features of t h i s react ion. Io7 Ac t iva t ion volumes f o r the subs t i tu t ion react ions o f both these anions have a lso been determined.lo8 The two c rys ta l lograph ica l l y independent molecules o f [ R U O S ~ H ~ ( C O ) ~ ~ ] e x h i b i t a wide range o f bent semi-bridging metal carbonyl bond parametersYfog and a l l confirm t o the Crabtree-Lavin empir ica l equation. lo Paramagnetism i n the even-electron c lus te r [ H ~ O S ~ O C ( C O ) ~ ~ ] has been studied,"' and v ib ra t iona l studies car r ied out on i n t e r s t i t i a l hydrides i n the metal carbonyls [Co6H(C0),,]-, [Nil2H(C0)2,l3- and

[N i 12H2(C0)21I2'. l2

clus ters w i t h ca. 40 metal atoms, show t h a t the r a d i i o f metal cores approach the dimensions of m e t a l l i c c r y s t a l l i t e s . An ana ly t i ca l e lec t ron microscopic study o f [Ni38Pt6H(C0)1+8] has now been reported, and a t low elect ron beam i n t e n s i t i e s , the e lect ron micrograph o f t h i s complex deposited as an MeCN so lu t ion on a carbon g r i d

The syntheses o f the [Re2H2(C0)8l2-

The c l u s t e r unsaturation o f t h i s 58 valence e lect ron moiety

The k i n e t i c s o f 13C0

K ine t ic measurements on the

Recent s t ruc tu re determinations on large metal carbonyl

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8: Metal Carbonyls 141

shows apparently uniform s ize spots corresponding t o the rad ius o f the m e t a l l i c core. formation o f a face-centred N i / P t alloy.113

A t high e lect ron beam in tens i t ies , p a r t i c l e agglomeration occurs w i t h the

Iod ina t ion o f [Mo(C0)412]2 a f fo rds a convenient en t ry i n t o mononuclear,

The preparation, octahedral Mo( I I1) complexes,114 and the react ion of [Re(CO)sF.ReFs] w i t h CO i n anhydrous HF has been used t o prepare [Re(C0)6][ReF6]. character isat ion and some reactions o f triosmium carbonyl c lus te rs containing both hydride and ha l ide l igands have been reported,l16 and 1 3 C n.m.r. studies car r ied out on a ser ies o f anionic rhodium carbonyl ha l ide species present i n aqueous s 0 1 u t i o n . l ~ ~ reductive carbonylat ion o f IrC13.3H20, which f i n a l l y y i e l d s Irb(C0)12, p u r i f i e d via the intermediacy o f the [Ir4(CO)1,1]- anion.11e

Carbonyl ha l ide species have a lso been in tercepted i n the

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