Sulfinato Iron(III) Complex for Electrocatalytic Proton Reduction

被引：47

作者：

Cavell, Andrew C. ^{[1
]}

Hartley, Carolyn L. ^{[1
]}

Liu, Dan ^{[1
]}

Tribble, Connor S. ^{[1
]}

McNamara, William R. ^{[1
]}

机构：

[1] Coll William & Mary, Dept Chem, Williamsburg, VA 23185 USA

来源：

INORGANIC CHEMISTRY | 2015年 / 54卷 / 07期

基金：

美国国家科学基金会;

关键词：

HYDROGENASE ACTIVE-SITE; FE-ONLY HYDROGENASE; MOLECULAR ELECTROCATALYSTS; FUNCTIONAL MODELS; GENERATING HYDROGEN; LOW OVERPOTENTIALS; NITRILE HYDRATASE; CRYSTAL-STRUCTURE; EVOLUTION; COBALT;

D O I：

10.1021/ic5030394

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

We report the first example of a sulfinato Fe(III) complex acting as a highly active electrocatalyst for proton reduction. The sulfinate binds to the metal through oxygen, resulting in a seven-membered chelate ring that is likely hemilabile during catalysis. Proton reduction occurs at -1.57 V versus Fc/Fc(+) in CH3CN with an i(c)/i(p) = 13 in CH3CN (k(obs) = 3300 s(-1)) and an overpotential of 800 mV. The catalysis is first order with respect to [catalyst] and second order with respect to [trifluoracetic acid]. An 11% increase in catalytic activity is observed in the presence of water, suggesting that sulfinate moieties are viable functional groups for aqueous proton reduction catalysts.

引用

页码：3325 / 3330

页数：6

共 43 条

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