Ni(III)(中位-5,7,7,12,14,14-六聚体- 1,1,4,8,11 -四氮杂环十四烷)在水溶液中氧化甲酸盐的机理研究

BioInorganic Reaction Mechanisms Pub Date : 1999-01-01 DOI:10.1515/irm-1999-0303

A. Meshulam, A. Masarwa, H. Cohen, D. Meyerstein

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引用次数: 1

摘要

标题三价镍配合物Ni(III)L在微酸性溶液中通过内球、单电子、速率决定步骤氧化甲酸盐。甲酸盐在Ni(III)L(H2O) (HCO2)+2中的氧化速率明显快于Ni(III)L(H2PO4)(HCO2-)+和Ni(III)L(HCO2-)+2中的氧化速率。结果表明，甲酸在这一过程中起着矛盾的作用;一方面它是还原剂，另一方面它稳定三价镍配合物。

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On the Mechanism of Oxidation of Formate by Ni(III) (meso-5,7,7,12,14,14-hexamethy 1-1,4,8,11 - tetraazacyclotetradecane) in Aqueous Solutions

Abstract The title trivalent nickel complex, Ni(III)L, oxidizes formate in slightly acidic solutions via an inner sphere, single electron, rate determining step. The rate of oxidation of the formate in Ni(III)L(H2O) (HCO2)+2 is considerably faster than in Ni(III)L(H2PO4 )(HCO2-)+ and in Ni(III)L(HCO2-)+2. The results point out that formate has an ambivalent role in this process; on the one hand it is the reducing agent but on the other hand it stabilizes the trivalent nickel complex.

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BioInorganic Reaction Mechanisms

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