Controlling Proton Delivery through Catalyst Structural Dynamics

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

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The fastest synthetic molecular catalysts for H2 production 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 H2 production rates for [Ni(PPh 2NC6H4R 2)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 H2 production 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 - Oct 17 2016

Fingerprint

Structural dynamics
Protons
Hydrogenase
Catalysts
Enzymes
Protonation
Ligands
Proteins
Oxidation

Keywords

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

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Controlling Proton Delivery through Catalyst Structural Dynamics. / Cardenas, Allan Jay P; Ginovska, Bojana; Kumar, Neeraj; Hou, Jianbo; Raugei, Simone; Helm, Monte; Appel, Aaron; Bullock, R Morris; O'Hagan, Molly.

In: Angewandte Chemie - International Edition, Vol. 55, No. 43, 17.10.2016, p. 13509-13513.

Research output: Contribution to journalArticle

Cardenas, Allan Jay P ; Ginovska, Bojana ; Kumar, Neeraj ; Hou, Jianbo ; Raugei, Simone ; Helm, Monte ; Appel, Aaron ; Bullock, R Morris ; O'Hagan, Molly. / Controlling Proton Delivery through Catalyst Structural Dynamics. In: Angewandte Chemie - International Edition. 2016 ; Vol. 55, No. 43. pp. 13509-13513.
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