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Title: O–O Radical Coupling: From Detailed Mechanistic Understanding to Enhanced Water Oxidation Catalysis

In this paper, a deeper mechanistic understanding of the key O–O bond formation step of water oxidation by the [Ru(bda)(L) 2] (bdaH 2 = 2,2'-bipyridine-6,6'-dicarboxylic acid; L is a pyridine or isoquinoline derivative) family of catalysts is reached through harmonious experimental and computational studies of two series of modified catalysts with systematic variations in the axial ligands. The introduction of halogen and electron-donating substituents in [Ru(bda)(4-X-py) 2] and [Ru(bda)(6-X-isq) 2] (X is H, Cl, Br, and I for the pyridine series and H, F, Cl, Br, and OMe for the isoquinoline series) enhances the noncovalent interactions between the axial ligands in the transition state for the bimolecular O–O coupling, resulting in a lower activation barrier and faster catalysis. From detailed transition state calculations in combination with experimental kinetic studies, we find that the main contributor to the free energy of activation is entropy due to the highly organized transition states, which is contrary to other reports. Previous work has considered only the electronic influence of the substituents, suggesting electron-withdrawing groups accelerate catalysis, but we show that a balance between polarizability and favorable π–π interactions is the key, leading to rationally devised improvements. Our calculations predict the catalysts with the lowestmore » ΔG for the O–O coupling step to be [Ru(bda)(4-I-py) 2] and [Ru(bda)(6,7-(OMe)2-isq) 2] for the pyridine and isoquinoline families, respectively. Our experimental results corroborate these predictions: the turnover frequency for [Ru(bda)(4-I-py) 2] (330 s –1) is a 10-fold enhancement with respect to that of [Ru(bda)(py) 2], and the turnover frequency for [Ru(bda)(6-OMe-isq) 2] reaches 1270 s –1, two times faster than [Ru(bda)(isq) 2].« less
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Publication Date:
Report Number(s):
BNL-209120-2018-JAAM
Journal ID: ISSN 0020-1669
Grant/Contract Number:
SC0012704; SC00112704
Type:
Published Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 17; 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). Chemical Sciences, Geosciences & Biosciences Division
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; water oxidation; ruthenium catalysts; halogen substituents; DFT calculations; stopped-flow kinetics; kinetic/mechanistic studies
OSTI Identifier:
1435374
Alternate Identifier(s):
OSTI ID: 1476288

Xie, Yan, Shaffer, David W., and Concepcion, Javier J.. O–O Radical Coupling: From Detailed Mechanistic Understanding to Enhanced Water Oxidation Catalysis. United States: N. p., Web. doi:10.1021/acs.inorgchem.8b00329.
Xie, Yan, Shaffer, David W., & Concepcion, Javier J.. O–O Radical Coupling: From Detailed Mechanistic Understanding to Enhanced Water Oxidation Catalysis. United States. doi:10.1021/acs.inorgchem.8b00329.
Xie, Yan, Shaffer, David W., and Concepcion, Javier J.. 2018. "O–O Radical Coupling: From Detailed Mechanistic Understanding to Enhanced Water Oxidation Catalysis". United States. doi:10.1021/acs.inorgchem.8b00329.
@article{osti_1435374,
title = {O–O Radical Coupling: From Detailed Mechanistic Understanding to Enhanced Water Oxidation Catalysis},
author = {Xie, Yan and Shaffer, David W. and Concepcion, Javier J.},
abstractNote = {In this paper, a deeper mechanistic understanding of the key O–O bond formation step of water oxidation by the [Ru(bda)(L)2] (bdaH2 = 2,2'-bipyridine-6,6'-dicarboxylic acid; L is a pyridine or isoquinoline derivative) family of catalysts is reached through harmonious experimental and computational studies of two series of modified catalysts with systematic variations in the axial ligands. The introduction of halogen and electron-donating substituents in [Ru(bda)(4-X-py)2] and [Ru(bda)(6-X-isq)2] (X is H, Cl, Br, and I for the pyridine series and H, F, Cl, Br, and OMe for the isoquinoline series) enhances the noncovalent interactions between the axial ligands in the transition state for the bimolecular O–O coupling, resulting in a lower activation barrier and faster catalysis. From detailed transition state calculations in combination with experimental kinetic studies, we find that the main contributor to the free energy of activation is entropy due to the highly organized transition states, which is contrary to other reports. Previous work has considered only the electronic influence of the substituents, suggesting electron-withdrawing groups accelerate catalysis, but we show that a balance between polarizability and favorable π–π interactions is the key, leading to rationally devised improvements. Our calculations predict the catalysts with the lowest ΔG‡ for the O–O coupling step to be [Ru(bda)(4-I-py)2] and [Ru(bda)(6,7-(OMe)2-isq)2] for the pyridine and isoquinoline families, respectively. Our experimental results corroborate these predictions: the turnover frequency for [Ru(bda)(4-I-py)2] (330 s–1) is a 10-fold enhancement with respect to that of [Ru(bda)(py)2], and the turnover frequency for [Ru(bda)(6-OMe-isq)2] reaches 1270 s–1, two times faster than [Ru(bda)(isq)2].},
doi = {10.1021/acs.inorgchem.8b00329},
journal = {Inorganic Chemistry},
number = 17,
volume = 57,
place = {United States},
year = {2018},
month = {4}
}