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Title: Noninnocent Proton-Responsive Ligand Facilitates Reductive Deprotonation and Hinders CO 2 Reduction Catalysis in [Ru(tpy)(6DHBP)(NCCH 3 )] 2+ (6DHBP = 6,6'-(OH) 2 bpy)

Ruthenium complexes with proton-responsive ligands [Ru(tpy)(nDHBP)(NCCH 3)](CF 3SO 3) 2 (tpy = 2,2':6',2"-terpyridine; nDHBP = n,n'-dihydroxy-2,2'-bipyridine, n = 4 or 6) were examined in this study for reductive chemistry and as catalysts for CO 2 reduction. Electrochemical reduction of [Ru(tpy)(nDHBP)(NCCH 3)] 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)(nDHBP–2H +)] 0) triggers catalysis of CO 2 reduction; however, the catalytic efficiency is strikingly lower than that of unsubstituted [Ru(tpy)(bpy)(NCCH 3)] 2+ (bpy = 2,2'-bipyridine). Cyclic voltammetry, bulk electrolysis, and spectroelectrochemical infrared experiments suggest the reactivity of CO 2 at both the Ru center and the deprotonated quinone-type ligand. Lastly, 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 CO 2.
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [3] ;  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry; Baruch College, New York, NY (United States). Department of Natural Science
  3. National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
Publication Date:
Report Number(s):
BNL-112052-2016-JA
Journal ID: ISSN 0020-1669; R&D Project: CO026; KC0304030
Grant/Contract Number:
SC00112704
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 9; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1335424

Duan, Lele, Manbeck, Gerald F., Kowalczyk, Marta, Szalda, David J., Muckerman, James T., Himeda, Yuichiro, and Fujita, Etsuko. Noninnocent Proton-Responsive Ligand Facilitates Reductive Deprotonation and Hinders CO2 Reduction Catalysis in [Ru(tpy)(6DHBP)(NCCH3 )]2+ (6DHBP = 6,6'-(OH)2 bpy). United States: N. p., Web. doi:10.1021/acs.inorgchem.6b00398.
Duan, Lele, Manbeck, Gerald F., Kowalczyk, Marta, Szalda, David J., Muckerman, James T., Himeda, Yuichiro, & Fujita, Etsuko. Noninnocent Proton-Responsive Ligand Facilitates Reductive Deprotonation and Hinders CO2 Reduction Catalysis in [Ru(tpy)(6DHBP)(NCCH3 )]2+ (6DHBP = 6,6'-(OH)2 bpy). United States. doi:10.1021/acs.inorgchem.6b00398.
Duan, Lele, Manbeck, Gerald F., Kowalczyk, Marta, Szalda, David J., Muckerman, James T., Himeda, Yuichiro, and Fujita, Etsuko. 2016. "Noninnocent Proton-Responsive Ligand Facilitates Reductive Deprotonation and Hinders CO2 Reduction Catalysis in [Ru(tpy)(6DHBP)(NCCH3 )]2+ (6DHBP = 6,6'-(OH)2 bpy)". United States. doi:10.1021/acs.inorgchem.6b00398. https://www.osti.gov/servlets/purl/1335424.
@article{osti_1335424,
title = {Noninnocent Proton-Responsive Ligand Facilitates Reductive Deprotonation and Hinders CO2 Reduction Catalysis in [Ru(tpy)(6DHBP)(NCCH3 )]2+ (6DHBP = 6,6'-(OH)2 bpy)},
author = {Duan, Lele and Manbeck, Gerald F. and Kowalczyk, Marta and Szalda, David J. and Muckerman, James T. and Himeda, Yuichiro and Fujita, Etsuko},
abstractNote = {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 in this study 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)(nDHBP–2H+)]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. Lastly, 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.},
doi = {10.1021/acs.inorgchem.6b00398},
journal = {Inorganic Chemistry},
number = 9,
volume = 55,
place = {United States},
year = {2016},
month = {4}
}