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Issue 7, 2014
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Controlling proton movement: electrocatalytic oxidation of hydrogen by a nickel(ii) complex containing proton relays in the second and outer coordination spheres

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Abstract

A nickel bis(diphosphine) complex containing proton relays in the second and outer coordination spheres, Ni(PCy2N(CH2)2OMe)2, (PCy2N(CH2)2OMe = 1,5-di(methoxyethyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane), is an electrocatalyst for hydrogen oxidation. The addition of hydrogen to the Ni(II) complex results in rapid formation of three isomers of the doubly protonated Ni(0) complex, [Ni(PCy2N(CH2)2OMe2H)2]2+. The three isomers show fast interconversion at 40 °C, unique to this complex in this class of catalysts. Under conditions of 1.0 atm H2 using H2O as a base, catalytic oxidation proceeds at a turnover frequency of 5 s−1 and an overpotential of 720 mV, as determined from the potential at half of the catalytic current. Compared to the previously reported Ni(PCy2NBn)2 complex, the new complex operates at a faster rate and at a lower overpotential.

Graphical abstract: Controlling proton movement: electrocatalytic oxidation of hydrogen by a nickel(ii) complex containing proton relays in the second and outer coordination spheres

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Article information


Submitted
30 Oct 2013
Accepted
24 Nov 2013
First published
03 Dec 2013

Dalton Trans., 2014,43, 2744-2754
Article type
Paper

Controlling proton movement: electrocatalytic oxidation of hydrogen by a nickel(II) complex containing proton relays in the second and outer coordination spheres

P. Das, M. Ho, M. O'Hagan, W. J. Shaw, R. Morris Bullock, S. Raugei and M. L. Helm, Dalton Trans., 2014, 43, 2744
DOI: 10.1039/C3DT53074D

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