title: Reduction of oxygen catalyzed by nickel diphosphine complexes with positioned pendant amines.
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 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.
authors.affiliation: Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352, USA.
authors.forename: Jenny Y
authors.initials: JY
authors.lastname: Yang
authors.forename: R Morris
authors.initials: RM
authors.lastname: Bullock
authors.forename: William G
authors.initials: WG
authors.lastname: Dougherty
authors.forename: W Scott
authors.initials: WS
authors.lastname: Kassel
authors.forename: Brendan
authors.initials: B
authors.lastname: Twamley
authors.forename: Daniel L
authors.initials: DL
authors.lastname: DuBois
authors.forename: M
authors.initials: M
authors.lastname: Rakowski DuBois
mesh_terms: D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D004563:Electrochemistry; D006859:Hydrogen / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D000588:Amines; D016877:Oxidants; D010720:Phosphines; D014867:Water; D009532:Nickel; D006859:Hydrogen; D006861:Hydrogen Peroxide; D010100:Oxygen