Synthesis of Diiron Hydrogenase Mimics Bearing Hydroquinone and Related Ligands. Electrochemical and Computational Studies of the Mechanism of Hydrogen Production and the Role of O-H . . . S Hydrogen Bonding

被引：73

作者：

Chen, Jinzhu ^{[1
]}

Vannucci, Aaron K. ^{[1
]}

Mebi, Charles A. ^{[1
]}

Okumura, Noriko ^{[1
]}

Borowski, Susan C. ^{[1
]}

Swenson, Matthew ^{[1
]}

Lockett, L. Tori ^{[1
]}

Evans, Dennis H. ^{[1
]}

Glass, Richard S. ^{[1
]}

Lichtenberger, Dennis L. ^{[1
]}

机构：

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

来源：

ORGANOMETALLICS | 2010年 / 29卷 / 21期

基金：

美国国家科学基金会;

关键词：

FE-ONLY HYDROGENASE; ACTIVE-SITE; PHOTOELECTRON-SPECTROSCOPY; REDOX POTENTIALS; WEAK ACIDS; REORGANIZATION; COORDINATION; GENERATION; REDUCTION; COMPLEXES;

D O I：

10.1021/om100396j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A new synthetic method for annulating hydroquinones to Fe2S2(CO)(6) moieties is reported. Piperidine catalyzed a multistep reaction between Fe-2(mu-SH)(2)(CO)(6) and quinones to afford bridged adducts in 26-76% yields. The hydroquinone adducts undergo reversible two-electron reductions. In the presence of acetic acid, hydrogen is produced catalytically with these adducts at potentials more negative than that of the initial reversible reduction. Spectroscopic studies suggest the presence of intramolecular hydrogen bonding between the phenolic OH groups and the adjacent sulfur atoms. Computations, which are in good agreement with the electrochemical studies and spectroscopic data, indicate that the hydrogen bonding is most important in the reduced forms of the catalysts. This hydrogen bonding lowers the reduction potential for catalysis but also lowers the basicity and thereby the reactivity of the catalysts.

引用

页码：5330 / 5340

页数：11

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