Syntheses and reactivity of aminobis(diorganylanylamino)phosphanes

Article abstract of DOI:10.1002/cber.19961290806

Aminobis(diorganylamino)phosphanes (R₂N)₂PNH₂ (R = JPr, c-Hex, PhJ (2a-c), were obtained by treatment of the corresponding chlorobis{diorganyiamino)phosphanes la-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 2 a with trimethyialane 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)]₂AlCl₂[AlCl ₄]^- (5), in which two imino-phosphorane moieties are linked by an A1C1₂ bridge. Lithiation of 2a and subsequent reaction with titanocene dichloride result in nudeophilic replacement of one chlorine atom to give the phosphanylamido-substituted titanocene compound (R₂N)₂P-N(H)Ti(Cl)Cp₂ (6a), which rearranges to its P-hydroiminophosphorane tautomer (R₂N)₂P(H)=NTi(Cl)Cp₂ (6b) on gentle heating. No isornerisation was observed in the case of N-borylated aminophosphane (R₂N)₂P-NH-(9-BBN) (7), obtained by reaction of lithiated 2a with B-C1-9-BBN. The X-ray structure analyses of compounds 2b, c, 3, 4, 5, and 6a are discussed. VCH Vorlagsgeselischaft mbH, 1996.