M. Driess, H. Pritzkow, Markus Skipinski
Nov 11, 1997
Citations
0
Influential Citations
45
Citations
Journal
Organometallics
Abstract
Metalation of the silyl(fluorosilyl)phosphane Is2(F)Si−PH(SiR3) (3a; Is = 2,4,6-triisopropylphenyl, R3Si = Me2(PriMe2C)Si) at phosphorus with NaN(SiMe3)2 (4) in the molar ratio of 1:1 in toluene leads to the solvent-free sodium derivative 1a which forms a Na2P2-dimer in solution and in the solid state. The coordinatively unsaturated Na centers are each additionally bonded to a fluorine atom, so that a ladder-like, puckered tricyclic F2Na2P2Si2 skeleton results as the central structural motif. The same conversion of 3a into 1a under less polar reaction conditions (hexane) and the complete conversion of the silyl(fluorosilyl)phosphane Is2(F)Si−PH(SiPri3) (3b) into its Na derivative 1b is kinetically hampered and can only be achieved if 2 equiv of sodium amide 4 are employed. Excess 4 may be recovered by fractional crystallization, from which its molecular Na3N3-trimer was isolated and structurally characterized for the first time. The unusual molecular polymeric cesium phosphanide [Is2(F)Si−PCs(SiPri3)·0.5T...