Bis‐Phosphaketenes LM(PCO)<sub>2</sub> (M=Ga, In): A New Class of Reactive Group 13 Metal‐Phosphorus Compounds
Mahendra K. Sharma, Pratima Dhawan, Christoph Helling, Christoph Wölper, Stephan Schulz
Abstract
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‐ 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).