Noninnocent Proton-Responsive Ligand Facilitates Reductive Deprotonation and Hinders CO2 Reduction Catalysis in [Ru(tpy)(6DHBP)(NCCH3)]2+ (6DHBP=6,6′-(OH)2bpy)

被引：38

作者：

Duan, Lele ^{[1
]}

Manbeck, Gerald F. ^{[1
]}

Kowalczyk, Marta ^{[1
]}

Szalda, David J. ^{[1
,2
]}

Muckerman, James T. ^{[1
]}

Himeda, Yuichiro ^{[3
]}

Fujita, Etsuko ^{[1
]}

机构：

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

[2] CUNY Bernard M Baruch Coll, Dept Nat Sci, 17 Lexington Ave, New York, NY 10010 USA

[3] Natl Inst Adv Ind Sci & Technol, Tsukuba Cent 5-1,1-1-1 Higashi, Tsukuba, Ibaraki 3058565, Japan

来源：

INORGANIC CHEMISTRY | 2016年 / 55卷 / 09期

基金：

日本科学技术振兴机构;

关键词：

MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; CARBON-DIOXIDE; ELECTROCHEMICAL REDUCTION; WATER-OXIDATION; PHOTOCATALYTIC REDUCTION; AQUEOUS-MEDIA; BASIS-SETS; RUTHENIUM; COMPLEXES;

D O I：

10.1021/acs.inorgchem.6b00398

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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.

引用

页码：4582 / 4594

页数：13

共 91 条

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