Neutral and Cationic Group 13 Alkyl and Hydride Complexes of a Phosphinimine−Amide Ligand

The phosphinimine−amine ligand 1 reacts with MR₃ (M = Al, Ga; R = Me, H) with loss of RH to form the complexes (i-Pr₂C₆H₃N)C(Me)CHPPh₂(NC₆H₃-i-Pr₂)MMe₂ (M = Al (2), Ga (3)) and (i-Pr₂C₆H₃N)C(Me)CHPPh₂(NC₆H₃-i-Pr₂)AlH₂(4). Subsequent reactions of 2 and 3 with [Ph₃C][B(C₆F₅)₄] afforded [(i-Pr₂C₆H₃N)C(Me)CHPPh₂(NC₆H₃-i-Pr₂)MMe][B(C₆F₅)₄] (M = Al (5), Ga (6)), while similar reactions of 2 and 3 with B(C₆F₅)₃ gave [(i-Pr₂C₆H₃N)C(Me)CHPPh₂(NC₆H₃-i-Pr₂)MMe][B(C₆F₅)₃Me] (M = Al (8), Ga (9)). The analogous reactions of 4 with [Ph₃C][B(C₆F₅)₄] and B(C₆F₅)₃ resulted in the formation of [(i-Pr₂C₆H₃N)C(Me)CHPPh₂(NC₆H₃-i-Pr₂)AlH][B(C₆F₅)₄] (10) and [(i-Pr₂C₆H₃N)C(Me)CHPPh₂(NC₆H₃-i-Pr₂)AlH][B(C₆F₅)₃H](11), respectively. Crystallographic studies of 1, 2, 4, and [(i-Pr₂C₆H₃N)C(Me)CHPPh₂(NC₆H₃-i-Pr₂)AlMe(OEt₂)][B(C₆F₅)₄](7) are reported.