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Updated: Oct 31, 2025
Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Phosphorus and Arsenic Atom Transfer to Isocyanides to Form π-Backbonding Cyanophosphide and Cyanoarsenide Titanium
Anders Reinholdt1, Mehrafshan G Jafari1, Christian Sandoval-Pauker2
1Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA, 19104, USA.
Abstract:
Decarbonylation along with E atom transfer from Na(OCE) (E=P, As) to an isocyanide coordinated to the tetrahedral TiII complex [(TptBu,Me )TiCl], yielded the [(TptBu,Me )Ti(η3 -ECNAd)] species (Ad=1-adamantyl, TptBu,Me- =hydrotris(3-tert-butyl-5-methylpyrazol-1-yl)borate). In the case of E=P, the cyanophosphide ligand displays nucleophilic reactivity toward Al(CH3 )3 ; moreover, its bent geometry hints to a reduced Ad-NCP3- resonance contributor. The analogous and rarer mono-substituted cyanoarsenide ligand, Ad-NCAs3- , shows the same unprecedented coordination mode but with shortening of the N=C bond. As opposed to TiII , VII fails to promote P atom transfer to AdNC, yielding instead [(TptBu,Me )V(OCP)(CNAd)]. Theoretical studies revealed the rare ECNAd moieties to be stabilized by π-backbonding interactions with the former TiII ion, and their assembly to most likely involve a concerted E atom transfer between Ti-bound OCE- to AdNC ligands when studying the reaction coordinate for E=P.
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