Jump to main content
Jump to site search

Issue 7, 2014
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 30 Oct 2013, accepted on 24 Nov 2013 and first published on 03 Dec 2013


Article type: Paper
DOI: 10.1039/C3DT53074D
Citation: Dalton Trans., 2014,43, 2744-2754
  •   Request permissions

    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

Search articles by author

Spotlight

Advertisements