Solution-phase photochemistry of a [FeFe]hydrogenase model compound: evidence of photoinduced isomerisation

Rafal Kania, Pim W. J. M. Frederix, Joseph A. Wright, Rein V. Ulijn, Christopher J. Pickett, Neil T. Hunt

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The solution-phase photochemistry of the [FeFe] hydrogenase subsite model (mu-S(CH2)(3)S)Fe-2(CO)(4)(PMe3)(2) has been studied using ultrafast time-resolved infrared spectroscopy supported by density functional theory calculations. In three different solvents, n-heptane, methanol, and acetonitrile, relaxation of the tricarbonyl intermediate formed by UV photolysis of a carbonyl ligand leads to geminate recombination with a bias towards a thermodynamically less stable isomeric form, suggesting that facile interconversion of the ligand groups at the Fe center is possible in the unsaturated species. In a polar or hydrogen bonding solvent, this process competes with solvent substitution leading to the formation of stable solvent adduct species. The data provide further insight into the effect of incorporating non-carbonyl ligands on the dynamics and photochemistry of hydrogenase-derived biomimetic compounds. (C) 2012 American Institute of Physics. [doi:10.1063/1.3679387]

Original languageEnglish
Article number044521
Pages (from-to)-
Number of pages9
JournalJournal of Chemical Physics
Volume136
Issue number4
DOIs
Publication statusPublished - 28 Jan 2012

Keywords

  • photochemistry
  • photoinduced isomerisation
  • infrared spectroscopy

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