Controlling proton movement

Electrocatalytic oxidation of hydrogen by a nickel(ii) complex containing proton relays in the second and outer coordination spheres

Parthapratim Das, Ming Hsun Ho, Molly O'Hagan, Wendy J. Shaw, R Morris Bullock, Simone Raugei, Monte Helm

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

A nickel bis(diphosphine) complex containing proton relays in the second and outer coordination spheres, Ni(PCy 2N (CH2)2OMe)2, (PCy 2N (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(PCy 2N(CH2)2OMe 2H)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 H 2O 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(PCy 2NBn)2 complex, the new complex operates at a faster rate and at a lower overpotential.

Original languageEnglish
Pages (from-to)2744-2754
Number of pages11
JournalDalton Transactions
Volume43
Issue number7
DOIs
Publication statusPublished - Feb 21 2014

Fingerprint

Nickel
Isomers
Protons
Hydrogen
Oxidation
Electrocatalysts
Catalytic oxidation
Catalysts
1,5-diaza-3,7-diphosphacyclooctane

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Controlling proton movement : Electrocatalytic oxidation of hydrogen by a nickel(ii) complex containing proton relays in the second and outer coordination spheres. / Das, Parthapratim; Ho, Ming Hsun; O'Hagan, Molly; Shaw, Wendy J.; Bullock, R Morris; Raugei, Simone; Helm, Monte.

In: Dalton Transactions, Vol. 43, No. 7, 21.02.2014, p. 2744-2754.

Research output: Contribution to journalArticle

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