Reduction of oxygen catalyzed by nickel diphosphine complexes with positioned pendant amines

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 con...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2010-01, Vol.39 (12), p.3001-3010
Main Authors: Yang, Jenny Y, Bullock, R Morris, Dougherty, William G, Kassel, W Scott, Twamley, Brendan, DuBois, Daniel L, Rakowski DuBois, M
Format: Article
Language:English
Subjects:
Amines
Amines - chemistry
Catalysis
Catalysts
Electrocatalysts
Electrochemistry
Enzymes
Hydrogen - chemistry
Hydrogen Peroxide - chemistry
Jewelry
Molecular Structure
Nickel
Nickel - chemistry
Oxidants - chemistry
Oxidation-Reduction
Oxygen - chemistry
Phosphines - chemistry
Reduction
Water - chemistry
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Summary: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.
ISSN:1477-9226
1477-9234
DOI:10.1039/b921245k