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Phosphirenium ions as masked phosphenium catalysts : mechanistic evaluation and application in synthesis
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dc.contributor.author | Gasperini, Danila | |
dc.contributor.author | Neale, Samuel E. | |
dc.contributor.author | Mahon, Mary F. | |
dc.contributor.author | MacGregor, Stuart A. | |
dc.contributor.author | Webster, Ruth L. | |
dc.date.accessioned | 2024-05-15T14:30:18Z | |
dc.date.available | 2024-05-15T14:30:18Z | |
dc.date.issued | 2021-05-07 | |
dc.identifier | 300485743 | |
dc.identifier | 5302e171-b65c-4166-882f-ae992d5cb4ad | |
dc.identifier | 85106620035 | |
dc.identifier.citation | Gasperini , D , Neale , S E , Mahon , M F , MacGregor , S A & Webster , R L 2021 , ' Phosphirenium ions as masked phosphenium catalysts : mechanistic evaluation and application in synthesis ' , ACS Catalysis , vol. 11 , no. 9 , pp. 5452-5462 . https://doi.org/10.1021/acscatal.1c01133 | en |
dc.identifier.issn | 2155-5435 | |
dc.identifier.other | ORCID: /0000-0003-3454-6776/work/156626225 | |
dc.identifier.uri | https://hdl.handle.net/10023/29889 | |
dc.description | The EPSRC is thanked for funding. S.E.N. thanks Heriot Watt University for the award of a James Watt scholarship. | en |
dc.description.abstract | The utilization of phosphirenium ions is presented; optimized and broadened three-membered ring construction is described together with the use of these ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes. Full characterization of the phosphirenium ions is presented, and initial experimental and computational mechanistic studies indicate that these act as a "masked phosphenium"source that is accessed via ring opening. Catalysis proceeds via associative transfer of {Ph2P+} to a carbonyl nucleophile, Hâ'SiR3 bond addition over the C=O group, and associative displacement of the product by a further equivalent of the carbonyl substrate, which completes the catalytic cycle. A competing off-cycle process leading to vinyl phosphine formation is detailed for the hydrosilylation of benzophenone for which an inverse order in [silane] is observed. Experimentally, the formation of side products, including off-cycle vinyl phosphine, is favored by electrondonating substituents on the phosphirenium cation, while catalytic hydrosilylation is promoted by electron-withdrawing substituents. These observations are rationalized in parallel computational studies. | |
dc.format.extent | 11 | |
dc.format.extent | 2098939 | |
dc.language.iso | eng | |
dc.relation.ispartof | ACS Catalysis | en |
dc.subject | Density functional theory | en |
dc.subject | Hydrosilylation | en |
dc.subject | Organocatalysis | en |
dc.subject | Phosphenium ions | en |
dc.subject | Phosphirenium ions | en |
dc.subject | Reaction mechanism studies | en |
dc.subject | Catalysis | en |
dc.subject | Chemistry(all) | en |
dc.subject | DAS | en |
dc.subject | AC | en |
dc.title | Phosphirenium ions as masked phosphenium catalysts : mechanistic evaluation and application in synthesis | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.identifier.doi | 10.1021/acscatal.1c01133 | |
dc.description.status | Peer reviewed | en |
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