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

Jenny Y. Yang; R. Morris Bullock; William G. Dougherty; W. Scott Kassel; Brendan Twamley; Daniel L. Dubois; M. Rakowski Dubois

doi:10.1039/b921245k

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

Jenny Y. Yang, R. Morris Bullock, William G. Dougherty, W. Scott Kassel, Brendan Twamley, Daniel L. Dubois, M. Rakowski Dubois

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article

63 Citations (Scopus)

Abstract

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 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 O₂ reduction. These results indicate that pendant bases in synthetic catalysts for O₂ 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.

Original language	English
Pages (from-to)	3001-3010
Number of pages	10
Journal	Dalton Transactions
Volume	39
Issue number	12
DOIs	https://doi.org/10.1039/b921245k
Publication status	Published - Mar 19 2010

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ASJC Scopus subject areas

Inorganic Chemistry

Cite this

Yang, J. Y., Bullock, R. M., Dougherty, W. G., Kassel, W. S., Twamley, B., Dubois, D. L., & Rakowski Dubois, M. (2010). Reduction of oxygen catalyzed by nickel diphosphine complexes with positioned pendant amines. Dalton Transactions, 39(12), 3001-3010. https://doi.org/10.1039/b921245k

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abstract = "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 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 O2 reduction. These results indicate that pendant bases in synthetic catalysts for O2 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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AU - Dubois, Daniel L.

AU - Rakowski Dubois, M.

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AB - 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 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 O2 reduction. These results indicate that pendant bases in synthetic catalysts for O2 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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10.1039/b921245k