Synthesis and Reactivity of Ga, In, Ge, and Sn Phosphaketenes

The synthesis of indium monophosphaketenes L 1 (X)InPCO (x = Cl 1a , Me 1b , L 1 = HC[C(Me)N(Ar)] 2 ; Ar = 2,6‐ i‐ Pr 2 C 6 H 3 ) and L 2 (Cl)InPCO ( 2a , L 2 = HC[C( t ‐Bu)N(Ar)] 2 ) and bisphosphaketene L 2 In(PCO) 2 ( 2b ) is reported. Redox reactions of 1a/2a with L 1 Ga gave L 1/2 In (L 1 3a , L 2 3b ) and L 1 (Cl)GaPCO ( 4 ), while reactions with heavy tetrylenes L 3 ECl (E = Ge, Sn, L 3 = PhC(N t ‐Bu) 2 ) resulted in Cl(Me)/PCO ligand exchange and formation of L 3 EPCO (E = Ge 5a , Sn 5b ). Oxidative addition of 5a/5b with L 1 Ga gave L 3 EGa(PCO)L 1 (M = Ge 6a , Sn 6b ). All compounds were characterized by heteronuclear ( 1 H, 13 C{ 1 H}, 31 P{ 1 H}) NMR spectroscopy, IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction (sc‐XRD, 1b , 2a , 3b , 6a ).