The Reaction of Cobaloximes with Hydrogen: Products and Thermodynamics

被引：111

作者：

Estes, Deven P. ^{[1
]}

Grills, David C. ^{[2
]}

Norton, Jack R. ^{[1
]}

机构：

[1] Columbia Univ, Dept Chem, New York, NY 10027 USA

[2] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 50期

关键词：

MOLECULAR-HYDROGEN; FUNCTIONAL MODELS; MECHANISM; ACTIVATION; EVOLUTION; KINETICS; COMPLEXES; HYDRIDOCOBALOXIME; DERIVATIVES; CATALYSTS;

D O I：

10.1021/ja508200g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A cobalt hydride has been proposed as an intermediate in many reactions of the Co(dmgBF(2))(2)L-2 system, but its observation has proven difficult. We have observed the UV-vis spectra of Co(dmgBF(2))(2)L-2 (1) in CH3CN under hydrogen pressures of up to 70 atm. A Co(I) compound (6a) with an exchangeable proton is eventually formed. We have determined the bond dissociation free energy and pK(a) of the new O-H bond in 6a to be 50.5 kcal/mol and 13.4, respectively, in CH3CN, matching previous reports.

引用

收藏

页码：17362 / 17365

页数：4

相关论文

共 29 条

[1] Cobaloximes as functional models for hydrogenases. 2. proton electroreduction catalyzed by difluoroborylbis(dimethylglyoximato)cobalt(II) complexes in organic media [J].

Baffert, Carole ;

Artero, Vincent ;

Fontecave, Marc .

INORGANIC CHEMISTRY, 2007, 46 (05) :1817-1824

[2] Combined Experimental-Theoretical Characterization of the Hydrido-Cobaloxime [HCo(dmgH)2(PnBu3)] [J].

Bhattacharjee, Anirban ;

Chavarot-Kerlidou, Murielle ;

Andreiadis, Eugen S. ;

Fontecave, Marc ;

Field, Martin J. ;

Artero, Vincent .

INORGANIC CHEMISTRY, 2012, 51 (13) :7087-7093

[3] MECHANISM OF HYDROGEN EVOLUTION FROM HYDRIDOCOBALOXIME [J].

CHAO, TH ;

ESPENSON, JH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (01) :129-133

[4] Mechanism of H2 Evolution from a Photogenerated Hydridocobaloxime [J].

Dempsey, Jillian L. ;

Winkler, Jay R. ;

Gray, Harry B. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (47) :16774-16776

[5] Kinetics of Electron Transfer Reactions of H2-Evolving Cobalt Diglyoxime Catalysts [J].

Dempsey, Jillian L. ;

Winkler, Jay R. ;

Gray, Harry B. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (03) :1060-1065

[6] Hydrogen Evolution Catalyzed by Cobaloximes [J].

Dempsey, Jillian L. ;

Brunschwig, Bruce S. ;

Winkler, Jay R. ;

Gray, Harry B. .

ACCOUNTS OF CHEMICAL RESEARCH, 2009, 42 (12) :1995-2004

[7]

Drago R.S., 1992, PHYS METHODS CHEM, V2nd

[8] A homogeneous system for the photogeneration of hydrogen from water based on a platinum(II) terpyridyl acetylide chromophore and a molecular cobalt catalyst [J].

Du, Pingwu ;

Knowles, Kathryn ;

Eisenberg, Richard .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (38) :12576-+

[9] Visible Light-Driven Hydrogen Production from Aqueous Protons Catalyzed by Molecular Cobaloxime Catalysts [J].

Du, Pingwu ;

Schneider, Jacob ;

Luo, Genggeng ;

Brennessel, William W. ;

Eisenberg, Richard .

INORGANIC CHEMISTRY, 2009, 48 (11) :4952-4962

[10] Mechanisms by which Alkynes React with CpCr(CO)3H. Application to Radical Cyclization [J].

Estes, Deven P. ;

Norton, Jack R. ;

Jockusch, Steffen ;

Sattler, Wesley .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (37) :15512-15518