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• 作者：Bruce ; Michael I. ; Halet ; Jean-Franç ; ois ; et. al.
• 关键词：Alkyne ; Carbon chain ; Carbyne ; Cluster ; Cobalt ; Tungsten
• 刊名：Journal of Organometallic Chemistry
• 出版年：1999
• 出版时间：April 22, 1999
• 年：1999
• 卷：578
• 期：1-2
• 页码：155-168
• 全文大小：289 K

文摘

Reactions of Co₂(CO)₈ with complexes M(CCCCR)(CO)₃Cp [M=Mo, W; R=H, Fe(CO)₂Cp] are described. Simple adducts containing a Co₂(CO)₆ group attached to the least sterically-hindered CC triple bond are formed. In contrast, when R=M(CO)₃Cp (M=Mo, W), bis-cluster complexes {Cp(OC)₈Co₂M(μ₃-C)}CC{(μ₃-C)Co₂M′(CO)₈Cp} (M=M′=Mo, W; M=Mo, M′=W) were obtained. All three complexes were structurally characterised. Important features are the presence of both distal and proximal Cp groups in each molecule, and the formal oxidation of the –CC–CC– chain in the precursor to C–CC–C system in the products. Extended Hückel and Density Functional Theory calculations have been used to rationalise the observed structures of the M₃C₄M₃ complexes. The reaction between Co₂(μ-dppm)(CO)₆ and {W(CO)₃Cp}₂(μ-C₄) gave the simple adduct Co₂(μ-dppm){μ-[Cp(OC)₃W]C₂CC[W(CO)₃Cp]}(CO)₄.