Incorporating peptides in the outer-coordination sphere of bioinspired electrocatalysts for hydrogen production

Avijita Jain, Sheri Lense, John C. Linehan, Simone Raugei, Herman Cho, Daniel L. Dubois, Wendy J. Shaw

Research output: Contribution to journalArticlepeer-review

61 Citations (Scopus)

Abstract

Four new cyclic 1,5-diaza-3,7-diphosphacyclooctane ligands have been prepared and used to synthesize [Ni(PPh2NR 2)2]2+ complexes in which R is a mono- or dipeptide. These complexes represent a first step in the development of an outer-coordination sphere for this class of complexes that can mimic the outer-coordination sphere of the active sites of hydrogenase enzymes. Importantly, these complexes retain the electrocatalytic activity of the parent [Ni(PPh2NPh2)2] 2+ complex in an acetonitrile solution with turnover frequencies for hydrogen production ranging from 14 to 25 s-1 in the presence of p-cyanoanilinium trifluoromethanesulfonate and from 135 to 1000 s-1 in the presence of protonated dimethylformamide, with moderately low overpotentials, ∼0.3 V. The addition of small amounts of water results in rate increases of 2-7 times. Unlike the parent complex, these complexes demonstrate dynamic structural transformations in solution. These results establish a building block from which larger peptide scaffolding can be added to allow the [Ni(PR2NR′2) 2]2+ molecular catalytic core to begin to mimic the multifunctional outer-coordination sphere of enzymes.

Original languageEnglish
Pages (from-to)4073-4085
Number of pages13
JournalInorganic Chemistry
Volume50
Issue number9
DOIs
Publication statusPublished - May 2 2011

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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