Theoretical and experimental investigation of the basicity of phosphino(silyl)carbenes

David Martin, Ona Illa, Antoine Baceiredo, Guy Bertrand, Rosa M. Ortuño, Vicenç Branchadell

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The reactivity of phosphino(trimethylsilyl)carbenes 1 with several organic acids has been examined in order to evaluate the pKa values of the conjugate acids. Carbenes 1 react efficiently with C-organic acids such as 1,3-dimesitylimidazolium chloride, phenylacetylene, acetonitrile, and acetyltrimethylsilane, which have pKa's in DMSO in the range 18-31. However, the reaction of the conjugate acids 1H+ with the anion perturbs the determination of the genuine basicity of 1. Theoretical calculations have been performed in order to quantify the basicity of phosphino(trimethylsilyl)-carbenes 1 and to compare them with that of N-heterocyclic carbenes 2. The pKa of 1H+ in DMSO has been computed to be in the 23.0-23.4 range, so that 1 is not strong enough as a base to spontaneously deprotonate organic acids such as phenylacetylene, acetonitrile, or acetyltrimethylsilane. However, its conjugate acid 1H + is a strong electrophile and easily reacts with the nucleophilic conjugate bases of these acids leading to the formation of the corresponding phosphorus ylides. © 2005 American Chemical Society.
Original languageEnglish
Pages (from-to)5671-5677
JournalJournal of Organic Chemistry
Issue number14
Publication statusPublished - 8 Jul 2005


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