Bis-Phosphaketenes LM(PCO)2 (M=Ga, In): A New Class of Reactive Group 13 Metal-Phosphorus Compounds.

Abstract

Phosphaketenes are versatile reagents in organophosphorus chemistry. We herein report on the synthesis of novel bis‐phosphaketenes, LM(PCO)2 (M=Ga 2 a, In 2 b; L=HC[C(Me)N(Ar)]2; Ar=2,6‐i‐Pr2C6H3) by salt metathesis reactions and their reactions with LGa to metallaphosphenes LGa(OCP)PML (M=Ga 3 a, In 3 b). 3 b represents the first compound with significant In−P π‐bonding contribution as was confirmed by DFT calculations. Compounds 3 a and 3 b selectively activate the N−H and O−H bonds of aniline and phenol at the Ga−P bond and both reactions proceed with a rearrangement of the phosphaethynolate group from Ga−OCP to M−PCO bonding. Compounds 2–5 are fully characterized by heteronuclear (1H, 13C{1H}, 31P{1H}) NMR and IR spectroscopy, elemental analysis, and single crystal X‐ray diffraction (sc‐XRD).