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Determination of the photolysis products of [FeFe]hydrogenase enzyme model systems using ultrafast multidimensional infrared spectroscopy

Stewart, Andrew I. and Wright, Joseph A. and Greetham, Gregory M. and Kaziannis, Spiridon and Santabarbara, Stefano and Towrie, Michael and Parker, Anthony W. and Pickett, Christopher J. and Hunt, Neil T. (2010) Determination of the photolysis products of [FeFe]hydrogenase enzyme model systems using ultrafast multidimensional infrared spectroscopy. Inorganic Chemistry, 49 (20). pp. 9563-9573. ISSN 0020-1669

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Abstract

Ultrafast transient 2D-IR (T-2D-IR) spectroscopy has been used to study the photolysis products of the [FeFe]hydrogenase enzyme model compound (mu-propanedithiolate)Fe-2(CO)(6) in heptane solution following irradiation at ultraviolet wavelengths. Observation of coupling patterns between the vibrational modes of the photoproduct species formed alongside examination of the appearance time scales of these signals has uniquely enabled assignment of the photoproduct spectrum to a single pentacarbonyl species. Comparison of the vibrational relaxation rate of the photoproduct with that of the parent is consistent with the formation of a solvent adduct at the vacant coordination site, while anisotropy data in conjunction with density functional theory simulations indicates substitution in an axial rather than equatorial position. No firm evidence of additional short-lived intermediates is seen, indicating that the subsequent chemistry of these species is likely to be strongly defined by the nature of the first solvation shell.

Item type: Article
ID code: 28973
Keywords: iron-only hydrogenase, effective core potentials, vobrational echo spectroscopy, active-site, molecular calculations, peptide, bond dynamics, Physical and theoretical chemistry, Physical and Theoretical Chemistry, Inorganic Chemistry
Subjects: Science > Chemistry > Physical and theoretical chemistry
Department: Faculty of Science > Physics
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Depositing user: Pure Administrator
Date Deposited: 28 Mar 2011 13:15
Last modified: 30 May 2014 05:02
URI: http://strathprints.strath.ac.uk/id/eprint/28973

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