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Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene

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Abstract

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.

Graphical abstract: Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene

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Publication details

The article was received on 25 Nov 2019, accepted on 29 Nov 2019 and first published on 02 Dec 2019


Article type: Edge Article
DOI: 10.1039/C9SC05969E
Chem. Sci., 2020, Advance Article
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Base induced isomerisation of a phosphaethynolato-borane: mechanistic insights into boryl migration and decarbonylation to afford a triplet phosphinidene

    D. W. N. Wilson, M. P. Franco, W. K. Myers, J. E. McGrady and J. M. Goicoechea, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC05969E

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