Controlling Proton Delivery through Catalyst Structural Dynamics

Allan Jay P. Cardenas, Bojana Ginovska, Neeraj Kumar, Jianbo Hou, Simone Raugei, Monte L. Helm, Aaron M. Appel, R. Morris Bullock, Molly O'Hagan

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

The fastest synthetic molecular catalysts for H2production and oxidation emulate components of the active site of hydrogenases. The critical role of controlled structural dynamics is recognized for many enzymes, including hydrogenases, but is largely neglected in designing synthetic catalysts. Our results demonstrate the impact of controlling structural dynamics on H2production rates for [Ni(PPh2NC6H4R2)2]2+catalysts (R=n-hexyl, n-decyl, n-tetradecyl, n-octadecyl, phenyl, or cyclohexyl). The turnover frequencies correlate inversely with the rates of chair–boat ring inversion of the ligand, since this dynamic process governs protonation at either catalytically productive or non-productive sites. These results demonstrate that the dynamic processes involved in proton delivery can be controlled through modification of the outer coordination sphere, in a manner similar to the role of the protein architecture in many enzymes. As a design parameter, controlling structural dynamics can increase H2production rates by three orders of magnitude with a minimal increase in overpotential.

Original languageEnglish
Pages (from-to)13509-13513
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number43
DOIs
Publication statusPublished - Jan 1 2016

Keywords

  • artificial enzymes
  • electrocatalysis
  • homogeneous catalysis
  • hydrogen production
  • structural dynamics

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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