Journal
DALTON TRANSACTIONS
Volume 39, Issue 12, Pages 3001-3010Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/b921245k
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Funding
- Office of Basic Energy Sciences of the Department of Energy
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Nickel(II) bis(diphosphine) complexes that contain positioned bases in the second coordination sphere have been found to catalyze the reduction of O-2 with H-2 to selectively form water. The complexes also serve as electrocatalysts for the reduction of O-2 with the addition of a weak acid. In contrast, a closely related nickel diphosphine complex without the positioned bases is catalytically inactive for O-2 reduction. These results indicate that pendant bases in synthetic catalysts for O-2 reduction can play a similar role to proton relays in enzymes, and that such relays should be considered in the design of catalysts for multi-electron and multi-proton reactions.
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