(NH)-phosphanylamido- and (PH)-phosphoraneiminato transition-metal complexes: Syntheses, structures, and computational studies

Reactions of aminobis(diorganylamino)phosphanes (R2N)(2)PNH2 (R = iPr (a), Cy (b)) with Cp2MCl2 (M = Ti, Zr, Hf), CpTiCl3, and TiCl4 lead to the forma tion of the transition-metal complexes (R2N)(2)PN(H)MCp2Cp2Cl (M=Ti (1b), Z r (2a,b) Hf (3a,b)) (R2N)(2)P(H)NTiCpCl2 (8a,b), and (R2N)(2)P(H)NTiCl3 (10 a,b), respectively. The influence of electronic effects of the metal fragme nt on the resulting equilibrium between the (NH)-phosphanylamido and the ta utomeric (PH-iminophosphorane form is presented in detail.; Computational s tudies unambiguously confirm the experimental results. The molecular struct ures of 2a, 3a, and 8b have been determined by single-crystal S-ray diffrac tion.