Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements
We carried out time-resolved infrared (TR-IR) and emission lifetime measurements on a Re(I) carbonyl complex having an N-heterocyclic carbene ligand, namely, fac-[Re(CO)3(PyImPh)Br], under photochemically reactive (in solution in acetonitrile) and nonreactive (in solution in dichloromethane) conditi...
| Main Authors: | , , , , , , , , |
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| Format: | Journal Article |
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American Chemical Society
2017
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| Online Access: | http://purl.org/au-research/grants/arc/FT130100033 http://hdl.handle.net/20.500.11937/51356 |
| _version_ | 1848758677676228608 |
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| author | Mukuta, T. Simpson, Peter Vaughan, Jamila Skelton, B. Stagni, S. Massi, Massimiliano Koike, K. Ishitani, O. Onda, K. |
| author_facet | Mukuta, T. Simpson, Peter Vaughan, Jamila Skelton, B. Stagni, S. Massi, Massimiliano Koike, K. Ishitani, O. Onda, K. |
| author_sort | Mukuta, T. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | We carried out time-resolved infrared (TR-IR) and emission lifetime measurements on a Re(I) carbonyl complex having an N-heterocyclic carbene ligand, namely, fac-[Re(CO)3(PyImPh)Br], under photochemically reactive (in solution in acetonitrile) and nonreactive (in solution in dichloromethane) conditions to investigate the mechanism of photochemical ligand substitution reactions. The TR-IR measurements revealed that no reaction occurs on a picosecond time scale and the cationic product, namely, fac-[Re(CO)3(PyImPh)(MeCN)](+), is produced on a nanosecond time scale only in solution in acetonitrile, which indicates that the reaction proceeds thermally from the excited state. Because no other products were observed by TR-IR, we concluded that this cationic product is an intermediate species for further reactions. The measurements of the temperature-dependent emission lifetime and analysis using transition-state theory revealed that the photochemical substitution reaction proceeds from a metal-to-ligand charge transfer excited state, the structure of which allows the potential coordination of a solvent molecule. Thus, the coordinating capacity of the solvent determines whether the reaction proceeds or not. This mechanism is different from those of photochemical reactions of other types of Re(I) carbonyl complexes owing to the unique characteristics of the carbene ligand. |
| first_indexed | 2025-11-14T09:47:48Z |
| format | Journal Article |
| id | curtin-20.500.11937-51356 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T09:47:48Z |
| publishDate | 2017 |
| publisher | American Chemical Society |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-513562018-02-28T05:52:58Z Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements Mukuta, T. Simpson, Peter Vaughan, Jamila Skelton, B. Stagni, S. Massi, Massimiliano Koike, K. Ishitani, O. Onda, K. We carried out time-resolved infrared (TR-IR) and emission lifetime measurements on a Re(I) carbonyl complex having an N-heterocyclic carbene ligand, namely, fac-[Re(CO)3(PyImPh)Br], under photochemically reactive (in solution in acetonitrile) and nonreactive (in solution in dichloromethane) conditions to investigate the mechanism of photochemical ligand substitution reactions. The TR-IR measurements revealed that no reaction occurs on a picosecond time scale and the cationic product, namely, fac-[Re(CO)3(PyImPh)(MeCN)](+), is produced on a nanosecond time scale only in solution in acetonitrile, which indicates that the reaction proceeds thermally from the excited state. Because no other products were observed by TR-IR, we concluded that this cationic product is an intermediate species for further reactions. The measurements of the temperature-dependent emission lifetime and analysis using transition-state theory revealed that the photochemical substitution reaction proceeds from a metal-to-ligand charge transfer excited state, the structure of which allows the potential coordination of a solvent molecule. Thus, the coordinating capacity of the solvent determines whether the reaction proceeds or not. This mechanism is different from those of photochemical reactions of other types of Re(I) carbonyl complexes owing to the unique characteristics of the carbene ligand. 2017 Journal Article http://hdl.handle.net/20.500.11937/51356 10.1021/acs.inorgchem.6b02936 http://purl.org/au-research/grants/arc/FT130100033 American Chemical Society fulltext |
| spellingShingle | Mukuta, T. Simpson, Peter Vaughan, Jamila Skelton, B. Stagni, S. Massi, Massimiliano Koike, K. Ishitani, O. Onda, K. Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements |
| title | Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements |
| title_full | Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements |
| title_fullStr | Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements |
| title_full_unstemmed | Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements |
| title_short | Photochemical Processes in a Rhenium(I) Tricarbonyl N-Heterocyclic Carbene Complex Studied by Time-Resolved Measurements |
| title_sort | photochemical processes in a rhenium(i) tricarbonyl n-heterocyclic carbene complex studied by time-resolved measurements |
| url | http://purl.org/au-research/grants/arc/FT130100033 http://hdl.handle.net/20.500.11937/51356 |