[Ni(P Me 2N Ph 2) 2] (BF 4) 2 as an electrocatalyst for H 2 production

Stefan Wiese, Uriah J. Kilgore, Daniel L. Dubois, R. Morris Bullock

Research output: Contribution to journalArticle

76 Citations (Scopus)

Abstract

A nickel(II) bis(diphosphine) complex, [Ni(P Me 2N Ph 2) 2](BF 4) 2 (P Me 2N Ph 2 = 1,5-diphenyl-3,7-dimethyl- 1,5-diaza-3,7-diphosphacyclooctane), has been synthesized and characterized. This complex, which contains pendant amines in the diphosphine ligand, is an electrocatalyst for hydrogen production by proton reduction. Using [(DMF)H]OTf as the acid, a turnover frequency of 1,540 s -1 was obtained with no added water, and a turnover frequency of 6,700 s -1 was found with 1.0 M water added. Thermochemical studies show that the hydride donor ability of [HNi(P Me 2N Ph 2) 2](BF 4) is δG° H- = 54.0 kcal/mol, and we estimate a driving force for H 2 elimination of 13.8 kcal/mol. [Ni(P Me 2N Ph 2) 2](BF 4) 2 is the fastest H 2 production catalyst in the [Ni(P R 2N R' 2) 2] (BF 4) 2 family of complexes.

Original languageEnglish
Pages (from-to)720-727
Number of pages8
JournalACS Catalysis
Volume2
Issue number5
DOIs
Publication statusPublished - May 4 2012

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Keywords

  • electrocatalysis
  • hydrogen
  • nickel
  • pendant amine
  • proton reduction
  • proton relay

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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