[(H2O)(terpy)Mn(μ-O)2Mn(terpy)(OH2)](NO3)3 (terpy = 2,2′:6,2′′-terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltammetry

Clyde W. Cady; Katherine E. Shinopoulos; Robert H. Crabtree; Gary W. Brudvig

doi:10.1039/B922087A

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[(H₂O)(terpy)Mn(μ-O)₂Mn(terpy)(OH₂)](NO₃)₃ (terpy = 2,2′:6,2′′-terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltammetry†

Clyde W. Cady,‡^a Katherine E. Shinopoulos,^a Robert H. Crabtree*^a and Gary W. Brudvig*^a

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* Corresponding authors

^a Department of Chemistry, Yale University, PO Box 208107, New Haven, CT, USA
E-mail: gary.brudvig@yale.edu, robert.crabtree@yale.edu

Abstract

Photosynthetic water oxidation occurs naturally at a tetranuclear manganese center in the photosystem II protein complex. Synthetically mimicking this tetramanganese center, known as the oxygen-evolving complex (OEC), has been an ongoing challenge of bioinorganic chemistry. Most past efforts have centered on water-oxidation catalysis using chemical oxidants. However, solar energy applications have drawn attention to electrochemical methods. In this paper, we examine the electrochemical behavior of the biomimetic water-oxidation catalyst [(H₂O)(terpy)Mn(μ-O)₂Mn(terpy)(H₂O)](NO₃)₃ [terpy = 2,2′:6′,2′′-terpyridine] (1) in water under a variety of pH and buffered conditions and in the presence of acetate that binds to 1 in place of one of the terminal water ligands. These experiments show that 1 not only exhibits proton-coupled electron-transfer reactivity analogous to the OEC, but also may be capable of electrochemical oxidation of water to oxygen.

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Article information

DOI: https://doi.org/10.1039/B922087A
Article type: Paper
Submitted: 22 Oct 2009
Accepted: 19 Feb 2010
First published: 17 Mar 2010

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Dalton Trans., 2010,39, 3985-3989

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[(H₂O)(terpy)Mn(μ-O)₂Mn(terpy)(OH₂)](NO₃)₃ (terpy = 2,2′:6,2′′-terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltammetry

C. W. Cady, K. E. Shinopoulos, R. H. Crabtree and G. W. Brudvig, Dalton Trans., 2010, 39, 3985 DOI: 10.1039/B922087A

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Dalton Transactions