Multiple-timescale photoreactivity of a model compound related to the active site of [FeFe]-hydrogenase

Anna R. Ridley; A. Ian Stewart; Katrin Adamczyk; Hirendra N. Ghosh; Boutheïna Kerkeni; Z. Xiao Guo; Erik T. J. Nibbering; Christopher Pickett; Neil Hunt

doi:10.1021/ic800568k

Multiple-timescale photoreactivity of a model compound related to the active site of [FeFe]-hydrogenase

Anna R. Ridley, A. Ian Stewart, Katrin Adamczyk, Hirendra N. Ghosh, Boutheïna Kerkeni, Z. Xiao Guo, Erik T. J. Nibbering, Christopher Pickett, Neil Hunt

Research output: Contribution to journal › Article › peer-review

38 Citations (Scopus)

Abstract

Ultraviolet (UV) photolysis of (µ-S(CH₂)₃S)Fe₂(CO)₆ (1), a model compound of the Fe-hydrogenase enzyme system, has been carried out. When ultrafast UV-pump infrared (IR)-probe spectroscopy, steady-state Fourier transform IR spectroscopic methods, and density functional theory simulations are employed, it has been determined that irradiation of 1 in an alkane solution at 350 nm leads to the formation of two isomers of the 16-electron complex (µ-S(CH₂)₃S)Fe₂(CO)₅ within 50 ps with evidence of a weakly associated solvent adduct complex. 1 is subsequently recovered on timescales covering several minutes. These studies constitute the first attempt to study the photochemistry and reactivity of these enzyme active site models in solution following carbonyl ligand photolysis.

Original language	English
Pages (from-to)	7453-7455
Number of pages	3
Journal	Inorganic Chemistry
Volume	47
Issue number	17
DOIs	https://doi.org/10.1021/ic800568k
Publication status	Published - 30 Jul 2008

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10.1021/ic800568k

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@article{11e46c912083462086c6ebcaa61f6495,

title = "Multiple-timescale photoreactivity of a model compound related to the active site of [FeFe]-hydrogenase",

abstract = "Ultraviolet (UV) photolysis of (µ-S(CH2)3S)Fe2(CO)6 (1), a model compound of the Fe-hydrogenase enzyme system, has been carried out. When ultrafast UV-pump infrared (IR)-probe spectroscopy, steady-state Fourier transform IR spectroscopic methods, and density functional theory simulations are employed, it has been determined that irradiation of 1 in an alkane solution at 350 nm leads to the formation of two isomers of the 16-electron complex (µ-S(CH2)3S)Fe2(CO)5 within 50 ps with evidence of a weakly associated solvent adduct complex. 1 is subsequently recovered on timescales covering several minutes. These studies constitute the first attempt to study the photochemistry and reactivity of these enzyme active site models in solution following carbonyl ligand photolysis.",

author = "Ridley, {Anna R.} and Stewart, {A. Ian} and Katrin Adamczyk and Ghosh, {Hirendra N.} and Bouthe{\"i}na Kerkeni and Guo, {Z. Xiao} and Nibbering, {Erik T. J.} and Christopher Pickett and Neil Hunt",

year = "2008",

month = jul,

day = "30",

doi = "10.1021/ic800568k",

language = "English",

volume = "47",

pages = "7453--7455",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "17",

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TY - JOUR

T1 - Multiple-timescale photoreactivity of a model compound related to the active site of [FeFe]-hydrogenase

AU - Ridley, Anna R.

AU - Stewart, A. Ian

AU - Adamczyk, Katrin

AU - Ghosh, Hirendra N.

AU - Kerkeni, Boutheïna

AU - Guo, Z. Xiao

AU - Nibbering, Erik T. J.

AU - Pickett, Christopher

AU - Hunt, Neil

PY - 2008/7/30

Y1 - 2008/7/30

N2 - Ultraviolet (UV) photolysis of (µ-S(CH2)3S)Fe2(CO)6 (1), a model compound of the Fe-hydrogenase enzyme system, has been carried out. When ultrafast UV-pump infrared (IR)-probe spectroscopy, steady-state Fourier transform IR spectroscopic methods, and density functional theory simulations are employed, it has been determined that irradiation of 1 in an alkane solution at 350 nm leads to the formation of two isomers of the 16-electron complex (µ-S(CH2)3S)Fe2(CO)5 within 50 ps with evidence of a weakly associated solvent adduct complex. 1 is subsequently recovered on timescales covering several minutes. These studies constitute the first attempt to study the photochemistry and reactivity of these enzyme active site models in solution following carbonyl ligand photolysis.

AB - Ultraviolet (UV) photolysis of (µ-S(CH2)3S)Fe2(CO)6 (1), a model compound of the Fe-hydrogenase enzyme system, has been carried out. When ultrafast UV-pump infrared (IR)-probe spectroscopy, steady-state Fourier transform IR spectroscopic methods, and density functional theory simulations are employed, it has been determined that irradiation of 1 in an alkane solution at 350 nm leads to the formation of two isomers of the 16-electron complex (µ-S(CH2)3S)Fe2(CO)5 within 50 ps with evidence of a weakly associated solvent adduct complex. 1 is subsequently recovered on timescales covering several minutes. These studies constitute the first attempt to study the photochemistry and reactivity of these enzyme active site models in solution following carbonyl ligand photolysis.

U2 - 10.1021/ic800568k

DO - 10.1021/ic800568k

M3 - Article

VL - 47

SP - 7453

EP - 7455

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 17

ER -