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

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‐ Pr 2 C 6 H 3 ) 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 ( 1 H, 13 C{ 1 H}, 31 P{ 1 H}) NMR and IR spectroscopy, elemental analysis, and single crystal X‐ray diffraction (sc‐XRD).