Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene
We report on the (tert-butyl)isocyanide-catalysed isomersation of a phosphaethynolato-borane, [B]OCP ([B] = N,N′-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), to its linkage isomer, a phosphaketenyl-borane, [B]PCO. Mechanistic insight into this unusual isomerisation was gained through...
| Main Authors: | , , , , |
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| Format: | Journal article |
| Language: | English |
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Royal Society of Chemistry
2019
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| _version_ | 1797068344368562176 |
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| author | Wilson, D Franco, M Myers, W McGrady, J Goicoechea, J |
| author_facet | Wilson, D Franco, M Myers, W McGrady, J Goicoechea, J |
| author_sort | Wilson, D |
| collection | OXFORD |
| description | We report on the (tert-butyl)isocyanide-catalysed isomersation of a phosphaethynolato-borane, [B]OCP ([B] = N,N′-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), to its linkage isomer, a phosphaketenyl-borane, [B]PCO. Mechanistic insight into this unusual isomerisation was gained through a series of stoichiometric reactions of [B]OCP with isocyanides and theoretical calculations at the Density Functional Theory (DFT) level. [B]PCO decarbonylates under photolytic conditions to afford a novel boryl-substituted diphosphene, [B]P[double bond, length as m-dash]P[B]. This reaction proceeds via a transient triplet phosphinidene which we have been able to observe spectroscopically by Electron Paramagnetic Resonance (EPR) spectroscopy. |
| first_indexed | 2024-03-06T22:09:24Z |
| format | Journal article |
| id | oxford-uuid:514882ec-af4a-4c16-8306-4601fadafe5b |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T22:09:24Z |
| publishDate | 2019 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | oxford-uuid:514882ec-af4a-4c16-8306-4601fadafe5b2022-03-26T16:18:39ZBase induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinideneJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:514882ec-af4a-4c16-8306-4601fadafe5bEnglishSymplectic Elements at OxfordRoyal Society of Chemistry2019Wilson, DFranco, MMyers, WMcGrady, JGoicoechea, JWe report on the (tert-butyl)isocyanide-catalysed isomersation of a phosphaethynolato-borane, [B]OCP ([B] = N,N′-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), to its linkage isomer, a phosphaketenyl-borane, [B]PCO. Mechanistic insight into this unusual isomerisation was gained through a series of stoichiometric reactions of [B]OCP with isocyanides and theoretical calculations at the Density Functional Theory (DFT) level. [B]PCO decarbonylates under photolytic conditions to afford a novel boryl-substituted diphosphene, [B]P[double bond, length as m-dash]P[B]. This reaction proceeds via a transient triplet phosphinidene which we have been able to observe spectroscopically by Electron Paramagnetic Resonance (EPR) spectroscopy. |
| spellingShingle | Wilson, D Franco, M Myers, W McGrady, J Goicoechea, J Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene |
| title | Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene |
| title_full | Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene |
| title_fullStr | Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene |
| title_full_unstemmed | Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene |
| title_short | Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene |
| title_sort | base induced isomerisation of a phosphaethynolato borane mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene |
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