Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase
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 t...
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| Format: | Article |
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American Chemical Society
2014
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| Online Access: | https://eprints.nottingham.ac.uk/29703/ |
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| author | 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 |
| author_facet | 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 |
| author_sort | Summers, Peter A. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T19:06:36Z |
| format | Article |
| id | nottingham-29703 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:06:36Z |
| publishDate | 2014 |
| publisher | American Chemical Society |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-297032020-05-04T16:46:27Z https://eprints.nottingham.ac.uk/29703/ 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 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. American Chemical Society 2014-04-22 Article PeerReviewed 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. and Schröder, Martin (2014) Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase. Inorganic Chemisry, 53 (9). pp. 4430-4439. ISSN 0020-1669 Hydrogenase rhenium nickel iron thiolate time-resolved IR proton reduction http://pubs.acs.org/doi/abs/10.1021/ic500089b doi:10.1021/ic500089b doi:10.1021/ic500089b |
| spellingShingle | Hydrogenase rhenium nickel iron thiolate time-resolved IR proton reduction 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 Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase |
| title | Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase |
| title_full | Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase |
| title_fullStr | Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase |
| title_full_unstemmed | Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase |
| title_short | Photochemical dihydrogen production using an analogue of the active site of [NiFe] hydrogenase |
| title_sort | photochemical dihydrogen production using an analogue of the active site of [nife] hydrogenase |
| topic | Hydrogenase rhenium nickel iron thiolate time-resolved IR proton reduction |
| url | https://eprints.nottingham.ac.uk/29703/ https://eprints.nottingham.ac.uk/29703/ https://eprints.nottingham.ac.uk/29703/ |