Mechanistic Studies on the Reductive Cyclooligomerisation of CO by U(III) Mixed Sandwich Complexes; the Molecular Structure of [(U(η-C8H6{SiiPr3

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• 作者：Alistair S. Frey ; F. Geoffrey N. Cloke ; Peter B. Hitchcock ; Iain J. Day ; Jennifer C. Green ; Georgina Aitken
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：October 22, 2008
• 年：2008
• 卷：130
• 期：42
• 页码：13816-13817
• 全文大小：136K
• 年卷期：v.130,no.42(October 22, 2008)
• ISSN：1520-5126

文摘

The stoichiometric reaction of 1 equiv of CO with [(U(η-C₈H₆{SiⁱPr₃-1,4}₂)(η-Cp*)] affords the linear diuranium ynediolate complex [(U(η-C₈H₆{SiⁱPr₃-1,4}₂)(η-Cp*)]₂(μ-η¹:η¹-C₂O₂) which does not react with further CO to give the deltate derivative [(U(η-C₈H₆{SiⁱPr₃-1,4}₂)(η-Cp*)]₂(μ-η¹:η²-C₃O₃). Spectroscopic and computational studies suggest a plausible mechanism for the formation of the deltate complex, in which a “zig-zag” diuranium ynediolate species is the key intermediate.