期刊
INORGANIC CHEMISTRY
卷 55, 期 9, 页码 4582-4594出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.6b00398
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资金
- U.S. Department of Energy, Office of Science, Division of Chemical Sciences, Geosciences, & Biosciences, Office of Basic Energy Sciences [DE-SC00112704]
- Japan Science and Technology Agency (JST), ACT-C
Ruthenium complexes with proton-responsive ligands [Ru(tpy)(nDHBP)(NCCH3)](CF3SO3)(2) (tpy = 2,2':6',2 ''-terpyridine; nDHBP = n,n'-dihydroxy-2,2'-bipyridine, n = 4 or 6) were examined for reductive chemistry and as catalysts for CO2 reduction. Electrochemical reduction of [Ru(tpy)(nDHBP)(NCCH3)](2+) generates deprotonated species through interligand electron transfer in which the initially formed tpy radical anion reacts with a proton source to produce singly and doubly deprotonated complexes that are identical to those obtained by base titration. A third reduction (i.e., reduction of [Ru(tpy)(nDHBP2H(+))](0)) triggers catalysis of CO2 reduction; however, the catalytic efficiency is strikingly lower than that of unsubstituted [Ru(tpy)(bpy)(NCCH3)](2+) (bpy = 2,2'-bipyridine). Cyclic voltammetry, bulk electrolysis, and spectroelectrochemical infrared experiments suggest the reactivity of CO2 at both the Ru center and the deprotonated quinone-type ligand. The Ru carbonyl formed by the intermediacy of a metallocarboxylic acid is stable against reduction, and mass spectrometry analysis of this product indicates the presence of two carbonates formed by the reaction of DHBP-2H(+) with CO2.
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