Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands

Xie, Yan; Shaffer, David W.; Lewandowska‐Andralojc, Anna; Szalda, David J.; Concepcion, Javier J.

doi:10.1002/ange.201601943

Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands

Journal Article · Wed May 11 00:00:00 EDT 2016 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201601943· OSTI ID:1400557

Xie, Yan ^[1]; Shaffer, David W. ^[1]; Lewandowska‐Andralojc, Anna ^[2]; Szalda, David J. ^[3]; Concepcion, Javier J. ^[1]

Chemistry Division Brookhaven National Laboratory Upton NY 11973-5000 USA
Chemistry Division Brookhaven National Laboratory Upton NY 11973-5000 USA, Faculty of Chemistry Adam Mickiewicz University Umultowska 89b 61614 Poznan Poland
Department of Natural Sciences Baruch College, CUNY New York NY 10010 USA

Abstract

We describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox‐potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH‐dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations. The unprecedented attack of water at a neutral six‐coordinate [Ru ^IV ] center to yield an anionic seven‐coordinate [Ru ^IV −OH] ⁻ intermediate is one of the key steps of a single‐site mechanism in which all species are anionic or neutral. These complexes are among the fastest single‐site catalysts reported to date.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1400557

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 28 Vol. 128; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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