Evidence for Formation of a Co鈥揌 Bond from (H2O)2Co(dmgBF2)2 under H2: Application to Radical Cyclizations

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• 作者：Gang Li ; Arthur Han ; Mary E. Pulling ; Deven P. Estes ; Jack R. Norton
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：September 12, 2012
• 年：2012
• 卷：134
• 期：36
• 页码：14662-14665
• 全文大小：289K
• 年卷期：v.134,no.36(September 12, 2012)
• ISSN：1520-5126

文摘

Under H₂, the radical cyclization of appropriate dienes can be catalyzed by cobaloximes. H鈥?can be abstracted from an intermediate (presumably a cobalt hydride) by trityl radicals (Ar₃C鈥? or by TEMPO. The rate-determining step in these reactions is the uptake of H₂, which is second order in cobalt and first order in hydrogen; the third-order rate constant is 106(3) M^鈥?路s^鈥?.