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

被引：105

作者：

Li, Gang ^{[1
]}

Han, Arthur ^{[1
]}

Pulling, Mary E. ^{[1
]}

Estes, Deven P. ^{[1
]}

Norton, Jack R. ^{[1
]}

机构：

[1] Columbia Univ, Dept Chem, New York, NY 10027 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 36期

关键词：

ELECTROCATALYTIC HYDROGEN EVOLUTION; N-HETEROCYCLIC CARBENE; ATOM TRANSFER; MOLECULAR CATALYST; ELECTRON-TRANSFER; COBALT; WATER; REDUCTION; KINETICS; ACTIVATION;

D O I：

10.1021/ja306037w

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Under H-2, the radical cyclization of appropriate dienes can be catalyzed by cobaloximes. H center dot can be abstracted from an intermediate (presumably a cobalt: hydride) by trityl radicals (Ar3C center dot) or by TEMPO. The rate-determining step in these reactions is the uptake of H-2, which is second order in cobalt and first order in hydrogen; the third-order rate constant is 106(3) M-2.s(-1).

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页码：14662 / 14665

页数：4

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