MULTIELECTRON-TRANSFER KINETICS FOR CIS-DIOXORHENIUM VERSUS TRANS-DIOXORHENIUM(V) SPECIES - ISOELECTRONIC MODELING WITH OSMIUM(VI/V) AND CONTROL OF INTERFACIAL REACTIVITY BY RHENIUM(IV) ACCESSIBILITY

被引：6

作者：

JONESSKEENS, LM ^{[1
]}

ZHANG, XL ^{[1
]}

HUPP, JT ^{[1
]}

机构：

[1] NORTHWESTERN UNIV,DEPT CHEM,EVANSTON,IL 60208

来源：

INORGANIC CHEMISTRY | 1992年 / 31卷 / 19期

关键词：

D O I：

10.1021/ic00045a005

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

cis- and trans-dioxorhenium(V) complexes containing ancillary (bi)pyridyl ligands are known to be reducible by two electrons with uptake of two protons in a single thermodynamic step. Interfacial electrochemical studies of these reactions by microelectrode techniques reveal that the electrochemical exchange kinetics are more than 100-fold faster for the cis complex than for the trans. Mechanistic studies, and careful comparisons to isoelectronic Os(VI) species, reveal that the cis/trans reactivity difference is due chiefly to a ca. 200 mV difference in thermodynamic accessibility to the intermediate Re(IV) oxidation state.

引用

页码：3879 / 3881

页数：3

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