Syntheses and reactivity of aminobis(diorganylamino)phosphanes

Aminobis(diorganylamino)phosphanes (R2N)2PNH2 (R = iPr, c-Hex, Ph) (2a–c), were obtained by treatment of the corresponding chlorobis(diorganylamino)phosphanes 1a–c with lithium amide in liquid ammonia. The transition metal phosphane complex (R2N)2(H2N)PNi(CO)3 (3) was prepared by reaction of 2a with tetracarbonylnickel. N-Complexation of 2a with trimethylalane affords the iminophosphorane-alane adduct (R2N)2HP=N(H)AlMe3 (4) by 1,2-H shift from the nitrogen to the phosphorus atom. The corresponding reaction with aluminium trichloride leads to the formation of the salt [(R2N)2HP=N(H)]2AlC12+[AlC14]− (5), in which two iminophosphorane moieties are linked by an AlCl2 bridge. Lithiation of 2a an…