Gallaphosphene L(Cl)GaPGaL: A novel phosphinidene transfer reagent

Abstract

Gallaphosphene L(Cl)GaPGaL 1 (L = HC[C(Me)N(Ar)]2; Ar = 2,6‐i‐Pr2C6H3) reacts with N‐heterocyclic carbenes RNHC (RNHC = [CMeN(R)]2C; R = Me, iPr) to RNHC‐coordinated phosphinidenes L(Cl)GaP←RNHC (R = Me 2a, iPr 2b) and with isonitriles RNC (R = iPr, Cy) to 1,3‐phosphaazaallenes L(Cl)GaP=C=N‐R (R = iPr 3a, Cy 3b), respectively. Quantum chemical calculations reveal that 2a/2b possesses two localized lone pair of electrons, whereas 3a/3b only show one localized lone pair as was reported for gallaphosphene 1. 2b reacts with 2.5 equivalents of a borane (THF•BH3) to the NHC‐stabilized phosphinidene‐borane complex [iPrNHC→P(BH2)]2(BH3)34 with concomitant formation of LGa(H)Cl 5. 2–5 are characterized by heteronuclear (1H, 13C{1H}, 31P{1H}) NMR and IR spectroscopy, elemental analysis, and single crystal X‐ray diffraction (sc‐XRD).