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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 O2 with H2 to selectively form water. The complexes also serve as electrocatalysts for the reduction of O2 with the addition of a weak acid. In contrast, a closely related nickel diphosphine complex without the positioned bases is catalytically inactive for O2reduction. These results indicate that pendant bases in synthetic catalysts for O2reduction 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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