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Title: Mononuclear ruthenium polypyridine complexes that catalyze water oxidation

Abstract

Over the past decade, significant advances have been made in the development of molecular water oxidation catalysts (WOCs) in the context of developing a system that would accomplish artificial photosynthesis. Mononuclear ruthenium complexes with polypyridine ligands have drawn considerable attention in this regard, due to their high catalytic activity and relatively simple structure. In this perspective review, we will discuss mononuclear Ru polypyridine WOCs by organizing them into four groups according to their ligand environments. Each group will be discussed with regard to three fundamental questions: first, how does the catalyst initiate O–O bond formation? Second, which step in the catalytic cycle is rate-determining? Third, how efficient is the catalyst according to the specific descriptors such as turnover frequency? All discussion is based on the high-valent ruthenium intermediates that are proposed in the catalytic cycle according to experimental observation and theoretical simulation. Two fundamental mechanisms are set forth. An acid–base mechanism that involves the attack of a water molecule on the oxo of a high valent Ru=O species to form the O–O bond. Subsequent steps lead to dissociation of O 2 and rehydration of the metal center. A second mechanism involves the formation of a Ru–O˙ radical species, two ofmore » which then couple to form a Ru–O–O–Ru species that can release O 2 afterwards. The acid–base mechanism appears to be more common and mechanistic differences could result from variation directly related to polypyridine ligand structures. Thus, understanding how electronic, steric, and conformational properties can effect catalyst performance will lead to the rational design of more effective WOCs with not only ruthenium but also other transition metals.« less

Authors:
 [1];  [2]
  1. Univ. of Houston, Houston, TX (United States). Dept. of Chemistry; Friedrich-Alexander Univ. of Erlangen–Nuremberg (FAU), Erlangen (Germany). Dept. of Chemistry and Pharmacy and Inorganic Chemistry
  2. Univ. of Houston, Houston, TX (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Houston, Houston, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); The Welch Foundation, Houston, TX (United States)
OSTI Identifier:
1434583
Grant/Contract Number:  
FG02-07ER15888; E-621
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 11; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 14 SOLAR ENERGY

Citation Formats

Tong, Lianpeng, and Thummel, Randolph P. Mononuclear ruthenium polypyridine complexes that catalyze water oxidation. United States: N. p., 2016. Web. doi:10.1039/c6sc02766k.
Tong, Lianpeng, & Thummel, Randolph P. Mononuclear ruthenium polypyridine complexes that catalyze water oxidation. United States. doi:10.1039/c6sc02766k.
Tong, Lianpeng, and Thummel, Randolph P. Fri . "Mononuclear ruthenium polypyridine complexes that catalyze water oxidation". United States. doi:10.1039/c6sc02766k. https://www.osti.gov/servlets/purl/1434583.
@article{osti_1434583,
title = {Mononuclear ruthenium polypyridine complexes that catalyze water oxidation},
author = {Tong, Lianpeng and Thummel, Randolph P.},
abstractNote = {Over the past decade, significant advances have been made in the development of molecular water oxidation catalysts (WOCs) in the context of developing a system that would accomplish artificial photosynthesis. Mononuclear ruthenium complexes with polypyridine ligands have drawn considerable attention in this regard, due to their high catalytic activity and relatively simple structure. In this perspective review, we will discuss mononuclear Ru polypyridine WOCs by organizing them into four groups according to their ligand environments. Each group will be discussed with regard to three fundamental questions: first, how does the catalyst initiate O–O bond formation? Second, which step in the catalytic cycle is rate-determining? Third, how efficient is the catalyst according to the specific descriptors such as turnover frequency? All discussion is based on the high-valent ruthenium intermediates that are proposed in the catalytic cycle according to experimental observation and theoretical simulation. Two fundamental mechanisms are set forth. An acid–base mechanism that involves the attack of a water molecule on the oxo of a high valent Ru=O species to form the O–O bond. Subsequent steps lead to dissociation of O2 and rehydration of the metal center. A second mechanism involves the formation of a Ru–O˙ radical species, two of which then couple to form a Ru–O–O–Ru species that can release O2 afterwards. The acid–base mechanism appears to be more common and mechanistic differences could result from variation directly related to polypyridine ligand structures. Thus, understanding how electronic, steric, and conformational properties can effect catalyst performance will lead to the rational design of more effective WOCs with not only ruthenium but also other transition metals.},
doi = {10.1039/c6sc02766k},
journal = {Chemical Science},
number = 11,
volume = 7,
place = {United States},
year = {Fri Aug 05 00:00:00 EDT 2016},
month = {Fri Aug 05 00:00:00 EDT 2016}
}

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Cited by: 33 works
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Works referenced in this record:

Catalytic Water Oxidation by Single-Site Ruthenium Catalysts
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