Journal
NATURE CHEMISTRY
Volume 5, Issue 4, Pages 293-299Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/NCHEM.1578
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Funding
- California Institute of Technology
- Searle Scholars Program
- NSF Graduate Research Fellowship Program
- NSF [CHE-1151918, CHE-0639094]
- NIH [F32GM100595]
- Office of Basic Energy Science (OBES), Division of Chemical Sciences, Geosciences, and Biosciences, DOE [DE-AC02-05CH11231]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1151918] Funding Source: National Science Foundation
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Redox-inactive metals are found in biological and heterogeneous water oxidation catalysts, but, at present, their roles in catalysis are not well understood. Here, we report a series of high-oxidation-state tetranuclear-dioxido clusters comprising three manganese centres and a redox-inactive metal (M). Crystallographic studies show an unprecedented Mn3M(mu(4)-O)(mu(2)-O) core that remains intact on changing M or the manganese oxidation state. Electrochemical studies reveal that the reduction potentials span a window of 700 mV and are dependent on the Lewis acidity of the second metal. With the pK(a) of the redox-inactive metal-aqua complex as a measure of Lewis acidity, these compounds demonstrate a linear dependence between reduction potential and acidity with a slope of similar to 100 mV per pK(a) unit. The Sr2+ and Ca2+ compounds show similar potentials, an observation that correlates with the behaviour of the oxygen-evolving complex of photosystem II, which is active only if one of these two metals is present.
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