On the Reactivity of Bisphosphirane‐Fused Anthracene towards Dichalcogenide Bonds, IPr Carbene, 2,6‐Diisopropylphenyl Isocyanide and Trimethylsilyl Azide

Abstract

The development of phosphinidene precursors capable of releasing free phosphinidenes holds great potential in exploiting their reactivity with small molecules and enthalpically strong bonds. We report the facile cleavage of dichalcogenide bonds, including S‐S, Se‐Se and Te‐Te bonded complexes over the phosphorus center of a bisphosphirane‐fused anthracene (1), which produces a variety of phosphonodichalcogenides (2‐4). We also show the ambiphilic nature of 1. The reaction of 1 with nucleophiles, such as 1,3‐bis(isopropyl)imidazol‐2‐ylidene (IiPr) and 2,6‐diisopropylphenyl isocyanide (DipNC) gives a phosphinidene adduct of IiPr and a 1‐phospha‐3‐azaallene, respectively. Treatment of 1 with trimethylsilyl azide (TMSN3) affords an iminophosphanide, manifesting the nucleophilic nature of 1. These compounds were fully characterized by single‐crystal X‐ray diffraction (SC‐XRD) and spectroscopic analysis.