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Electrochemical Reduction of CO 2 by M(CO) 4 (diimine) Complexes (M=Mo, W): Catalytic Activity Improved by 2,2′‐Dipyridylamine
Author(s) -
Franco Federico,
Cometto Claudio,
Sordello Fabrizio,
Minero Claudio,
Nencini Luca,
Fiedler Jan,
Gobetto Roberto,
Nervi Carlo
Publication year - 2015
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201500115
Subject(s) - diimine , chemistry , catalysis , acetonitrile , electrochemistry , denticity , cyclic voltammetry , bulk electrolysis , electrolysis , electrocatalyst , o phenylenediamine , inorganic chemistry , electrode , crystallography , organic chemistry , electrolyte , crystal structure
Tetracarbonyl complexes of low‐valent Group VI transition metals (Mo and W), containing diimine bidentate ligands, namely W(CO) 4 (4,6‐diphenyl‐2,2′‐bipyridine) ( 1 ), W(CO) 4 (6‐(2,6‐dimethoxyphenyl)‐4‐phenyl‐2,2′‐bipyridine) ( 2 ), Mo(CO) 4 (2,2′‐dipyridylamine) ( 3 ), and W(CO) 4 (2,2′‐dipyridylamine) ( 4 ), were synthesized and tested as homogeneous catalysts for the electrochemical reduction of CO 2 in nonaqueous media. Cyclic voltammetry performed under a CO 2 atmosphere, revealed that these complexes have significant catalytic activity in acetonitrile, and gas chromatographic measurements together with exhaustive electrolysis showed that CO is the major reduction product. Mechanistic insights were obtained by IR‐spectroelectrochemical measurements. The substantially different electrocatalytic performances obtained for the two classes of catalysts are compared and discussed.