Cobalt Clathrochelate Complexes as Hydrogen-Producing Catalysts

被引:117
作者
Pantani, Olivier [1 ]
Naskar, Subhendu [1 ]
Guillot, Regis [1 ]
Millet, Pierre [1 ]
Anxolabehere-Mallart, Elodie [1 ]
Aukauloo, Ally [1 ,2 ]
机构
[1] Univ Paris 11, CNRS, UMR 8182, ICMMO, F-91405 Orsay, France
[2] CEA Saclay, IBiTec S, F-91191 Gif Sur Yvette, France
关键词
chelates; cobalt; coordination compounds; electrocatalysis; hydrogen;
D O I
10.1002/anie.200803643
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Wrapper's delight: Clathrochelate complexes, in which the metal center is wrapped in a close-knit macrobicyclic ligand, are often considered to be deprived of chemical reactivity. Boron-capped cobalt tris(glyoximato) complexes show catalytic activity in the reduction of acids in acetonitrile at potentials as small as -0.5 V versus SCE. Alteration of ligand substituents allows for the tuning of their electrochemical reactivity (see structure: red ball Co, grey C, purple B, blue N, red O, green X). (Figure Presented) © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码:9948 / 9950
页数:3
相关论文
共 25 条
[1]   HOMOGENEOUS REDOX CATALYSIS OF ELECTROCHEMICAL REACTIONS .5. CYCLIC VOLTAMMETRY [J].
ANDRIEUX, CP ;
BLOCMAN, C ;
DUMASBOUCHIAT, JM ;
MHALLA, F ;
SAVEANT, JM .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1980, 113 (01) :19-40
[2]   Molybdenum-sulfur dimers as electrocatalysts for the production of hydrogen at low overpotentials [J].
Appel, AM ;
DuBois, DL ;
DuBois, MR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (36) :12717-12726
[3]   CHARACTERIZATION OF THE STRUCTURE, PROPERTIES, AND REACTIVITY OF A COBALT(II) MACROCYCLIC COMPLEX [J].
BAKAC, A ;
BRYNILDSON, ME ;
ESPENSON, JH .
INORGANIC CHEMISTRY, 1986, 25 (23) :4108-4114
[4]   Electrochemistry of macrocyclic cobalt(III/II) hexaamines: Electrocatalytic hydrogen evolution in aqueous solution [J].
Bernhardt, PV ;
Jones, LA .
INORGANIC CHEMISTRY, 1999, 38 (22) :5086-5090
[5]   Homogeneous catalysis of electrochemical hydrogen evolution by iron(0) porphyrins [J].
Bhugun, I ;
Lexa, D ;
Saveant, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (16) :3982-3983
[7]   MECHANISM OF HYDROGEN EVOLUTION FROM HYDRIDOCOBALOXIME [J].
CHAO, TH ;
ESPENSON, JH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (01) :129-133
[8]   Hydrogen production by molecular photocatalysis [J].
Esswein, Arthur J. ;
Nocera, Daniel G. .
CHEMICAL REVIEWS, 2007, 107 (10) :4022-4047
[9]   Fundamental properties of small molecule models of Fe-only hydrogenase: computations relative to the definition of an entatic state in the active site [J].
Georgakaki, IP ;
Thomson, LM ;
Lyon, EJ ;
Hall, MB ;
Darensbourg, MY .
COORDINATION CHEMISTRY REVIEWS, 2003, 238 :255-266
[10]   Cooperating ligands in catalysis [J].
Griitzmacher, Hansjoerg .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (10) :1814-1818