Treatment of Silylene–Phosphinidene with Chalcogens Resulted Exclusively in the Formation of Silicon‐Bonded Chalcogens

Abstract

Abstract Chalcogen‐bonded silicon phosphinidenes LSi(E)−P−MecAAC (E=S (1); Se (2); Te (3); L=PhC(NtBu)2; MecAAC=C(CH2)(CMe2)2N‐2,6‐iPr2C6H3)) were synthesized from the reactions of silylene–phosphinidene LSi−P−MecAAC (A) with elemental chalcogens. All the compounds reported herein have been characterized by multinuclear NMR, elemental analyses, LIFDI‐MS, and single‐crystal X‐ray diffraction techniques. Furthermore, the regeneration of silylene–phosphinidene (A) was achieved from the reactions of 2–3 with L′Al (L′=HC{(CMe)(2,6‐iPr2C6H3N)}2). Theoretical studies on chalcogen‐bonded silicon phosphinidenes indicate that the Si−E (E=S, Se, Te) bond can be best represented as charge‐separated electron‐sharing σ‐bonding interaction between [LSi−P−MecAAC]+ and E−. The partial double‐bond character of Si−E is attributed to significant hyperconjugative donation from the lone pair on E− to the Si−N and Si−P σ ‐molecular orbitals.

Join the main‐group meeting: Chalcogen‐bonded silicon(IV) phosphinidenes LSi(E)−P−MecAAC (E=S, Se, Te) were synthesized from the reactions of silylene–phosphinidene LSi−P−MecAAC with elemental chalcogens. These are the first molecular examples in which a Si=E group is attached to a phosphinidene moiety. All the compounds were characterized by single‐crystal X‐ray structural analysis. image