A low-valent dinuclear ruthenium diazadiene complex catalyzes the oxidation of dihydrogen and reversible hydrogenation of quinones

被引：9

作者：

Yang, Xiuxiu ^{[1
]}

Gianetti, Thomas L. ^{[1
,2
]}

Woerle, Michael D. ^{[1
]}

van Leest, Nicolaas P. ^{[3
]}

de Bruin, Bas ^{[3
]}

Grutzmacher, Hansjoerg ^{[1
]}

机构：

[1] Swiss Fed Inst Technol, Dept Chem & Appl Biosci, Vladimir Prelog Weg 1, CH-8093 Zurich, Switzerland

[2] Univ Arizona, Dept Chem & Biochem, Tucson, AZ 85721 USA

[3] Univ Amsterdam, Vant Hoff Inst Mol Sci HIMS, Sci Pk 904, NL-1098 XH Amsterdam, Netherlands

来源：

CHEMICAL SCIENCE | 2019年 / 10卷 / 04期

基金：

瑞士国家科学基金会;

关键词：

FE-ONLY HYDROGENASE; NICKEL-IRON HYDROGENASE; ACTIVE-SITE; CRYSTAL-STRUCTURE; NIFE HYDROGENASE; METAL-COMPLEX; H-2; MODEL; REDUCTION; ELECTROCATALYST;

D O I：

10.1039/c8sc02864h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The dinuclear ruthenium complex [Ru2H(mu-H)(Me(2)dad)(dbcot)(2)] contains a 1,4-dimethyl-diazabuta-1,3-diene (Me(2)dad) as a non-innocent bridging ligand between the metal centers to give a [Ru-2(Me(2)dad)] core. In addition, each ruthenium is bound to one dibenzo[a,e]cyclooctatetraene (dbcot) ligand. This Ru dimer converts H-2 to protons and electrons. It also catalyzes reversibly under mild conditions the selective hydrogenation of vitamins K-2 and K-3 to their corresponding hydroquinone equivalents without affecting the C=C double bonds. Mechanistic studies suggest that the [Ru-2(Me(2)dad)] moiety, like hydrogenases, reacts with H-2 and releases electrons and protons stepwise.

引用

页码：1117 / 1125

页数：9

共 58 条

[1] A hybrid density functional theory molecular mechanics study of nickel-iron hydrogenase: Investigation of the active site redox states [J].