Summers, Peter A. and Dawson, Joe and Ghiotto, Fabio and Hanson-Heine, Magnus W. D. and Vuong, Khuong Q. and Davies, E. Stephen and Sun, Xue-Z. and Besley, Nicholas A. and McMaster, Jonathan and George, Michael W. and Schröder, Martin
Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase.
Inorganic Chemisry, 53
The photoproduction of dihydrogen (H2) by a low molecular weight analogue of the active site of [NiFe] hydrogenase has been investigated by the reduction of the [NiFe2] cluster, 1, by a photosensitier PS (PS = [ReCl(CO)3(bpy)] or [Ru(bpy)3][PF6]2). Reductive quenching of the 3MLCT excited state of the photosensitiser by NEt3 or N(CH2CH2OH)3 (TEOA) generates PS•−, and subsequent intermolecular electron transfer to 1 produces the reduced anionic form of 1. Time-resolved infrared spectroscopy (TRIR) has been used to probe the intermediates throughout the reduction of 1 and subsequent photocatalytic H2 production from [HTEOA][BF4], which was monitored by gas chromatography. Two structural isomers of the reduced form of 1 (1a•− and 1b•−) were detected by Fourier transform infrared spectroscopy (FTIR) in both CH3CN and DMF (dimethylformamide), while only 1a•− was detected in CH2Cl2. Structures for these intermediates are proposed from the results of density functional theory calculations and FTIR spectroscopy. 1a•− is assigned to a similar structure to 1 with six terminal carbonyl ligands, while calculations suggest that in 1b•− two of the carbonyl groups bridge the Fe centres, consistent with the peak observed at 1714 cm−1 in the FTIR spectrum for 1b•− in CH3CN, assigned to a ν(CO) stretching vibration. The formation of 1a•− and 1b•− and the production of H2 was studied in CH3CN, DMF and CH2Cl2. Although the more catalytically active species (1a•− or 1b•−) could not be determined, photocatalysis was observed only in CH3CN and DMF.
||This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemisry, copyright © American Chemical Society after peer review. To access the final edited and published work, see http://pubs.acs.org/doi/abs/10.1021/ic500089b
||Hydrogenase, rhenium, nickel, iron, thiolate, time-resolved IR, proton reduction
||University of Nottingham, UK > Faculty of Science > School of Chemistry
||27 Aug 2015 09:45
||25 Apr 2017 05:56
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