Syntheses and X-ray Structures of Novel Main Group Bis(dialkylamino)phosphinimides
作者:S. Schulz、M. Raab、M. Nieger、E. Niecke
DOI:10.1021/om000059e
日期:2000.6.1
Reactions of aminobis(dicyclohexylamino)phosphane with several aluminum trialkyls R3Al (R = Me, Et, t-Bu) yield the simple Lewis acid−base adducts (Cy2N)2P(H)N(H)AlR3 (R = Me, 1; Et, 2; t-Bu, 3). Dimeric phosphiniminoalanes [(Cy2N)2P(H)NAlR2]2 (R = Me, 4; Et, 5) were obtained by reactions of aminobis(dicyclohexylamino)phosphane with the corresponding dialkyl aluminum hydride R2AlH. X-ray structure
(NH)-Phosphanylamido- and (PH)-Phosphoraneiminato Transition-Metal Complexes: Syntheses, Structures, and Computational Studies
作者:Michael Raab、Andreas Sundermann、Gerold Schick、Armin Loew、Martin Nieger、Wolfgang W. Schoeller、Edgar Niecke
DOI:10.1021/om000967b
日期:2001.4.1
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 formation of the transition-metal complexes (R2N)(2)PN(H)MCp2Cp2Cl (M=Ti (1b), Zr (2a,b) Hf (3a,b)) (R2N)(2)P(H)NTiCpCl2 (8a,b), and (R2N)(2)P(H)NTiCl3 (10a,b), respectively. The influence of electronic effects of the metal fragment on the resulting equilibrium between the (NH)-phosphanylamido and the tautomeric (PH-iminophosphorane form is presented in detail.; Computational studies unambiguously confirm the experimental results. The molecular structures of 2a, 3a, and 8b have been determined by single-crystal S-ray diffraction.
Syntheses and Reactivity of Aminobis(diorganylamino)phosphanes
lithium amide in liquidammonia. 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
The first oligomeric phosphazene in which each phosphorus center features a PH functionality (3) was obtained from the amidophosphane 1 or its zirconium complex 2.