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Selective formation of ketones by electrochemical reduction of CO 2 catalyzed by ruthenium complexes
Author(s) -
Tanaka Koji,
Mizukawa Tetsunori
Publication year - 2000
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/1099-0739(200012)14:12<863::aid-aoc88>3.0.co;2-4
Subject(s) - chemistry , ruthenium , electrochemistry , nucleophile , catalysis , bond cleavage , intramolecular force , denticity , reagent , medicinal chemistry , photochemistry , redox , metal , inorganic chemistry , organic chemistry , electrode
Electrochemical reduction of CO 2 aimed at carbon–carbon bond formation was examined. Polypyridyl–ruthenium–carbonyl complexes catalyze electrochemical reduction of CO 2 to produce CO and CO 3 2− in organic solvents. Among those metal complexes, a ruthenium carbonyl complex with monodentate naphthy‐ridine showed a unique redox behavior. One‐electron reduction of the complex resulted in intramolecular nucleophilic attack of the non‐bonded nitrogen of naphthyridine to the carbonyl carbon to form a five‐membered ring. Such metallacyclization greatly served for activation of the RuCO bond derived from CO 2 without accompanying reductive cleavage of the bond (CO evolution). Electrochemical reduction of CO 2 catalyzed by [Ru(bpy)(napy) 2 (CO) 2 ] 2+ in the presence of (CH 3 ) 4 NBF 4 produced only CH 3 C(O)CH 3 and CO 3 2− , where (CH 3 ) 4 N + worked as not only the electrolyte but also the methylation reagent. Copyright © 2000 John Wiley & Sons, Ltd.