Countercations and Solvent Influence CO2 Reduction to Oxalate by Chalcogen-Bridged Tricopper Cyclophanates

被引：41

作者：

Cook, Brian J. ^{[1
,2
]}

Di Francesco, Gianna N. ^{[1
]}

Abboud, Khalil A. ^{[1
]}

Murray, Leslie J. ^{[1
,2
]}

机构：

[1] Univ Florida, Ctr Catalysis, Gainesville, FL 32611 USA

[2] Univ Florida, Florida Ctr Heterocycl Cpds, Dept Chem, Gainesville, FL 32611 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 17期

关键词：

CARBON-DIOXIDE REDUCTION; FRUSTRATED LEWIS PAIRS; ELECTROCHEMICAL REDUCTION; MOLECULAR CATALYSTS; OXYGEN REDUCTION; NICKEL-COMPLEXES; ACTIVE-SITE; COPPER; METAL; MECHANISM;

D O I：

10.1021/jacs.8b02508

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

One-electron reduction of Cu3EL (L3- = tris(beta-diketiminate)cyclophane, and E = S, Se) affords [Cu3EL](-), which reacts with CO2 to yield exclusively C2O42- (95% yield, TON = 24) and regenerate Cu3EL. Stopped-flow UV/visible data support an A -> B mechanism under pseudo-first-order conditions (k(obs), (298K) = 115(2) s(-1)), which is 10(6) larger than those for reported copper complexes. The k(obs) values are dependent on the countercation and solvent (e.g., k(obs) is greater for [K(18-crown-6)](+) vs (Ph3P)(2)N+, and there is a 20-fold decrease in k(obs) in THF vs DMF). Our results suggest a mechanism in which cations and solvent influence the stability of the transition state.

引用

页码：5696 / 5700

页数：5

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