Alkynes [C2Ph2, MeC2Ph, PhC2H, and C2(CO2Et)2] displace the bridging GePh2 group from [(OC)3Co(μ-GePh2)(μ-CO)Co(CO)3], (I), to form the well known complexes [(OC)3(Co(μ-alkyne)Co(CO)3] together with (GePh2)n (n = 4-7). The kinetics of reaction of complex (I) with diphenylacetylene in decalin have been studied over a range of temperature. The rate of reaction is first order in [Complex] and [C2Ph2] and the reaction is greatly retarded by carbon monoxide. The results are consistent with a reaction mechanism that involves initial reversible ring opening to form [(OC)3Co(μ-GePh2)Co(CO)4], a process that is also involved in a reactions of complex (I) with carbon monoxide and triphenyl- and tributyl-phosphine. A mechanism involving intermediates with terminally co-ordinated GePh2 groups cannot be conclusively ruled out but is considered to be less probable.

Reaction mechanisms of metal-metal bonded carbonyls. Part VII. Reaction of alkynes with μ-carbonyl-μ-diphenylgermanio-bis(tricarbonylcobalt)(Co-Co)

BASATO, MARINO;
1974

Abstract

Alkynes [C2Ph2, MeC2Ph, PhC2H, and C2(CO2Et)2] displace the bridging GePh2 group from [(OC)3Co(μ-GePh2)(μ-CO)Co(CO)3], (I), to form the well known complexes [(OC)3(Co(μ-alkyne)Co(CO)3] together with (GePh2)n (n = 4-7). The kinetics of reaction of complex (I) with diphenylacetylene in decalin have been studied over a range of temperature. The rate of reaction is first order in [Complex] and [C2Ph2] and the reaction is greatly retarded by carbon monoxide. The results are consistent with a reaction mechanism that involves initial reversible ring opening to form [(OC)3Co(μ-GePh2)Co(CO)4], a process that is also involved in a reactions of complex (I) with carbon monoxide and triphenyl- and tributyl-phosphine. A mechanism involving intermediates with terminally co-ordinated GePh2 groups cannot be conclusively ruled out but is considered to be less probable.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11577/2519021
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