摘要:
NUMBER 1, 1967 7 A Cobalt-Cobalt Bond Supported by Bridging Tin and Carbonyl Groups By D. J. PATMORE and W. A. G. GRAHAM (Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada) KUMEROUS compounds have been reported in which tetracarbonylcobalt groups are bonded to four-co- ordinate tin : Ph,SnCo(CO),,l CI,S~[CO(CO),],,~ and MeSn[Co(CO),] 33 will serve as examples. We now report a cobalt carbonyl derivative of six-co- ordinate tin with some novel structural features. Reaction of bis (acetylacetonato) dichlorotin (IV) with tetracarbonylcobalt (-I) anion affords a moder- ately stable red crystalline compound, m.p. 86-88’ (decomp.) . Analysis indicates a composition (C,H,O,),SnCo,(CO),, and this formula is confirmed by an exact mass determination on the 632 peak of the Co-Sn-Co bond angle is larger than in the six- co-ordinate compound (I).J 3 8 CO k&-CO 0.1 4 Sn f \ c o o’dc>coc H3C H3C&b ? ‘ 0 CH? the mass spectrum. In cyclohexane, the infrared spectrum shows terminal carbonyl stretching bands a t 2076 (m), 2036 (s), 2013 (s), 2004 (m), and 1994 (m) cm.-l, and one band a t 1836 (m) cm.-l which can be ascribed to a bridging carbonyl group. Several bands in the 1500-1600 cm.-l region can be assigned to (CZO) and (C’ZC) in the acetylaceto- nato-ring~.~ The compound is essentially dia- magnetic. On the above evidence, we suggest structure (I) Structure (I) can be derived from that of cobalt carbonyl by replacing one bridging CO with the (C,H,O,),Sn group; from this point of view it is related to the carbon-bridged structure of CO,(CO),HC=CH.~ In relation to the general structural type represented by (11) (MI M‘ metal .. for the compound. A cobalt-cobalt bond is the cobalt atoms, and we represent this bond as required to preserve the inert-gas configuration for “bent” to suggest an octahedral geometry around the cobalt atoms. The formation of (I) can be \ / regarded as a displacement of chloride ions from M ’ 1 ‘w (OC) n (11) M (C,H,O,),SnCl, (which most probably has the cis- configuration5) to give cis-(C,H,O,),Sn[Co(CO),],. Spontaneous loss of CO and Co-Co bond formation atoms, the number Of bridging co groups), then lock the molecule in the cis-form. compound (I) is believed to provide the first Isolation of such a compound supports our example with 12 = 1.in which f l = 0 suggestion3 that similar bridged species are formed are 0s3(c0)12~7 and a with M=Fe readily in the mass spectrometer from XSn [Co- and M’=Sn.* The solid-state of Fe, (co)i, (C0),l3 and X,[Co(CO),],; for these molecules, the is Of (I1) where = 2, a molecular ion was not detected, and the most related heterocyclic case (M = Fe, M’ = Mn),is con- abundant ion was lighter by one CO group. Under sidered to be present in the anion ~nFe2(CO)121-.10 (Received, November 8th, 1966; Com. 868.) ordinary conditions, these derivatives of four-co- ordinate tin do not lose CO, presumably because F. Hein and W. Jehn, Annalen, 1965, 684. 4. a D. J. Patmore and W. A. G. Graham, Inorg. Chem., 1966, 5, 1405; F. Bonati, S. Cenini, D. Morelli, and R. Ugo, a D. J . Patmore and W. A. G. Graham, Inorg. Nuclear Chem. Letters, 1966, 2, 179; Inorg. Chem., in the press. K. Nakamoto, “Infrared Spectra of Inorganic and Coordination Compounds,” Wiley, New York, 1963, p. 216. J. A. S. Smith and E. J. Wilkins, Chem. Comm., 1965, 381. 0. S. Mills and G. Robinson, Proc. Chem. Soc., 1959, 166. E. R. Corey and L. F. Dahl, Inorg. Chem., 1962, 1, 521. C. H. Wei and L. F. Dahl, J . Amer. Chem. Soc., 1966, 88, 1821. J . Chem. SOC. (A), 1966, 1052. * J . D. Cotton, J . Duckworth, S. A. R. Knox, P. F. Lindley, I. Paul, F. G. A. Stone, and P. Woodward, Chem. Comm., 1966, 253. lo U. Anders and W. A. G. Graham, Chem. Comm., 1966, 291.
ISSN:0009-241X
DOI:10.1039/C19670000007
出版商:RSC
年代:1967
数据来源: RSC