The Library
Photoactivation of titanium-oxo cluster [Ti 6 O 6 (OR) 6 (O 2 C t Bu) 6 ] : mechanism, photoactivated structures, and onward reactivity with O 2 to a peroxide complex
Tools
Tools
Tools
Brown, Stephen E., Mantaloufa, Ioanna, Andrews, Ryan T., Barnes, Thomas J., Lees, Martin R., De Proft, Frank, Cunha, Ana V. and Pike, Sebastian D. (2023) Photoactivation of titanium-oxo cluster [Ti 6 O 6 (OR) 6 (O 2 C t Bu) 6 ] : mechanism, photoactivated structures, and onward reactivity with O 2 to a peroxide complex. Chemical Science, 14 (3). pp. 675-683. doi:10.1039/d2sc05671b ISSN 2041-6539.
|
PDF
WRAP-photoactivation-titanium-oxo-cluster-2022.pdf - Published Version - Requires a PDF viewer. Available under License Creative Commons Attribution. Download (1206Kb) | Preview |
Official URL: https://doi.org/10.1039/d2sc05671b
Abstract
The molecular titanium-oxo cluster [Ti6O6(OiPr)6(O2CtBu)6] (1) can be photoactivated by UV light, resulting in a deeply coloured mixed valent (photoreduced) Ti (iii/iv) cluster, alongside alcohol and ketone (photooxidised) organic products. Mechanistic studies indicate that a two-electron (not free-radical) mechanism occurs in this process, which utilises the cluster structure to facilitate multielectron reactions. The photoreduced products [Ti6O6(OiPr)4(O2CtBu)6(sol)2], sol = iPrOH (2) or pyridine (3), can be isolated in good yield and are structurally characterized, each with two, uniquely arranged, antiferromagnetically coupled d-electrons. 2 and 3 undergo onward oxidation under air, with 3 cleanly transforming into peroxide complex, [Ti6O6(OiPr)4(O2CtBu)6(py)(O2)] (5). 5 reacts with isopropanol to regenerate the initial cluster (1) completing a closed cycle, and suggesting opportunities for the deployment of these easily made and tuneable clusters for sustainable photocatalytic processes using air and light. The redox reactivity described here is only possible in a cluster with multiple Ti sites, which can perform multi-electron processes and can adjust its shape to accommodate changes in electron density.
| Item Type: | Journal Article | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| Subjects: | Q Science > QD Chemistry | ||||||||
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Physics |
||||||||
| SWORD Depositor: | Library Publications Router | ||||||||
| Library of Congress Subject Headings (LCSH): | Titanium-oxo, Chemistry, Inorganic, Peroxides, Oxidation | ||||||||
| Journal or Publication Title: | Chemical Science | ||||||||
| Publisher: | The Royal Society of Chemistry | ||||||||
| ISSN: | 2041-6539 | ||||||||
| Official Date: | 21 January 2023 | ||||||||
| Dates: |
|
||||||||
| Volume: | 14 | ||||||||
| Number: | 3 | ||||||||
| Page Range: | pp. 675-683 | ||||||||
| DOI: | 10.1039/d2sc05671b | ||||||||
| Status: | Peer Reviewed | ||||||||
| Publication Status: | Published | ||||||||
| Access rights to Published version: | Open Access (Creative Commons) | ||||||||
| Date of first compliant deposit: | 16 December 2022 | ||||||||
| Date of first compliant Open Access: | 16 December 2022 | ||||||||
| RIOXX Funder/Project Grant: |
|
Request changes or add full text files to a record
Repository staff actions (login required)
 |
View Item |
Downloads
Downloads per month over past year
