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通过速率决定的质子耦合电子转移到双核钴-μ-1,2-过氧配合物，实现 O2 的四电子催化还原。

Catalytic four-electron reduction of O2 via rate-determining proton-coupled electron transfer to a dinuclear cobalt-μ-1,2-peroxo complex.

机构信息

Department of Material and Life Science, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.

出版信息

J Am Chem Soc. 2012 Jun 20;134(24):9906-9. doi: 10.1021/ja303674n. Epub 2012 Jun 8.

DOI:10.1021/ja303674n
PMID:22656065
Abstract

Four-electron reduction of O(2) by octamethylferrocene (Me(8)Fc) occurs efficiently with a dinuclear cobalt-μ-1,2-peroxo complex, 1, in the presence of trifluoroacetic acid in acetonitrile. Kinetic investigations of the overall catalytic reaction and each step in the catalytic cycle showed that proton-coupled electron transfer from Me(8)Fc to 1 is the rate-determining step in the catalytic cycle.

摘要

四电子还原 O(2) 由八甲基二茂铁 (Me(8)Fc) 与双核钴-μ-1,2-过氧配合物 1 在三氟乙酸存在下在乙腈中高效发生。对总催化反应和催化循环中每个步骤的动力学研究表明，Me(8)Fc 向 1 的质子耦合电子转移是催化循环中的速控步骤。

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