A Crystalline Phosphorus-Substituted Borinium Ion: Double Dihydrogen Activation by an Ambiphilic Inorganic Allene

Abstract

We report the synthesis of the first monomeric, isolable ambiphilic borinium ion. Bromide abstraction from a bromo(diphosphino)borane precursor affords a two-coordinate boron cation with a structure isolobal to allene. The presence of two phosphido substituents directly bonded to the boron center provides electronic stabilization, enabling the isolation of the P-substituted borinium ion in crystalline form. This compound readily forms adducts with N-heterocyclic carbenes, yielding diphosphinoborenium ions. The ambiphilic nature of the P-substituted borinium ion is demonstrated by its ability to activate dihydrogen under mild, catalyst-free conditions, highlighting its dual Lewis acidic and basic character.