Supramolecular Assembly Promotes the Electrocatalytic Reduction of Carbon Dioxide by Re(I) Bipyridine Catalysts at a Lower Overpotential

被引：129

作者：

Machan, Charles W. ^{[1
]}

Chabolla, Steven A. ^{[1
]}

Yin, Jian ^{[2
]}

Gilson, Michael K. ^{[2
]}

Tezcan, F. Akif ^{[1
]}

Kubiak, Clifford P. ^{[1
]}

机构：

[1] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA

[2] Univ Calif San Diego, Skaggs Sch Pharm & Pharmaceut Sci, La Jolla, CA 92093 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 41期

关键词：

CO2; REDUCTION; ELECTRON-TRANSFER; ELECTROCHEMICAL REDUCTION; HYDROGEN-BONDS; RE-RE; DEHYDROGENASE; COMPLEXES; FORMATE; ELECTROREDUCTION; SELECTIVITY;

D O I：

10.1021/ja5085282

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The addition of methyl acetamidomethyl groups at the 4,4'-positions of a 2,2'-bipyridyl ligand is found to enhance the rate of a bimolecular reduction mechanism of CO2 by Re(II)fac-tricarbonyl chloride complexes. Electrochemical studies, spectroelectrochemical measurements, and molecular dynamics simulations indicate that these methyl acetamidomethyl groups promote the formation of a hydrogen-bonded dimer. This supramolecular complex catalyzes the reductive disproportionation of CO2 to CO and CO32- at a lower overpotential (ca. 250 mV) than the corresponding single-site 2 e- reduction of CO2 to CO and H2O catalyzed by the corresponding model complex with a 4,4'-dimethyl-2,2'-bipyridyl ligand. These findings demonstrate that noncovalent self-assembly can modulate the catalytic properties of metal complexes by favoring alternate catalytic pathways.

引用

页码：14598 / 14607

页数：10