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Photochemical Dihydrogen Production Using an Analogue of the Active Site of [NiFe] Hydrogenase

Summers, Peter A.; Dawson, Joe; Ghiotto, Fabio; Hanson-Heine, Magnus W.D.; Vuong, Khuong Q.; Davies, E. Stephen; Sun, Xue-Z.; Besley, Nicholas A.; McMaster, Jonathan; George, Michael W.; Schröder, Martin

Authors

Peter A. Summers

Joe Dawson

Fabio Ghiotto

Khuong Q. Vuong

Nicholas A. Besley

Martin Schröder



Abstract

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.

Citation

Summers, P. A., Dawson, J., Ghiotto, F., Hanson-Heine, M. W., Vuong, K. . Q., Davies, E. S., …Schröder, M. (2014). Photochemical Dihydrogen Production Using an Analogue of the Active Site of [NiFe] Hydrogenase. Inorganic Chemistry, 53(9), 4430-4439. https://doi.org/10.1021/ic500089b

Journal Article Type Article
Online Publication Date Apr 22, 2014
Publication Date May 5, 2014
Deposit Date Aug 27, 2015
Publicly Available Date Aug 27, 2015
Journal Inorganic Chemistry
Print ISSN 0020-1669
Electronic ISSN 1520-510X
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 53
Issue 9
Pages 4430-4439
DOI https://doi.org/10.1021/ic500089b
Keywords Hydrogenase, rhenium, nickel, iron, thiolate, time-resolved IR, proton reduction
Public URL http://eprints.nottingham.ac.uk/id/eprint/29703
Publisher URL http://pubs.acs.org/doi/abs/10.1021/ic500089b
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf
Additional Information Received 14 January 2014

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

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Copyright Statement
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Copyright Statement
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