Binuclear Complexes Containing a Methylnickel Moiety: Relevance to Organonickel Intermediates in Acetyl Coenzyme A Synthase Catalysis

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• 作者：William G. Dougherty ; Krishnan Rangan ; Molly J. O’ ; Hagan ; Glenn P. A. Yap ; Charles G. Riordan
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：October 15, 2008
• 年：2008
• 卷：130
• 期：41
• 页码：13510-13511
• 全文大小：156K
• 年卷期：v.130,no.41(October 15, 2008)
• ISSN：1520-5126

文摘

A series of binuclear NiNi complexes supported by a single thiolate bridge and containing a methylnickel moiety have been prepared and fully characterized. The complexes represent structural analogues for the proposed organonickel intermediate in the acetyl coenzyme A synthase catalytic cycle. Variable temperature ³¹P NMR spectroscopy was used to examine dynamic behavior of the thiolate bridging interaction in two of the derivatives. Kinetic analyses, independent exchange and crossover experiments support an intermolecular exchange mechanism. Carbonylation results in thioester formation via a reductive elimination pathway.