Synthesen und Strukturen von cyclischen und acyclischen Vanadium(V)‐ und Molbydän(VI)‐haltigen Verbindungen

Abstract

Syntheses and Structures of Cyclic and Acyclic Compounds Containing Vanadium(V) and Molybdenum(V1)The reaction of (CzF5)2P(C1) = NSiMe3 (2) with C13V = NSiMe, in CHzClz yields the eight-membered ring [(C2F5) SiMe3I4 (6) and (CF,),P(CI) = N -MoOCl, (7), respectively. The molecular structures of 3, 5, and 6 have been determined by X-ray diffraction.Seit einigen Jahren beschaftigen wir uns rnit der Synthese von sechs-und achtgliedrigen ungesattigten anorganischen Ringsystemen, in denen einzelne Heteroatome durch Ubergangsmetalle substituiert sind. 1986 beschrieben wir den ersten sechsgliedrigen Wolfram-haltigen Phosphazenring'). Danach haben wir uber entsprechende Vanadium-, Niob-, Molybdan-und Rhenium-haltige Verbindungen berichtet ' 1.

Synthesis and Characterization of Vanadium(V)−Phosphinimide Complexes

“…Relatively few vanadium(V)−phosphinimide complexes have been reported previously. The reactions of VOX 3 (X = Cl, F) with Me 3 SiNPR 3 have led to a variety of vanadium(V)−phosphinimide complexes such as VOCl 2 (NPPh 3 ), VOCl(NPPh 3 ) 2 , VCl 3 (NPPh 3 ) 2 , VOF 2 (NPPh 3 ), VOCl 2 (NPPh 2 NS(O)Me 2 ), VCl 2 (N(NPPh 2 ) 2 ), and VCl 2 (NP(CF 3 ) 2 NP(CF 3 )NP(CF 3 ) 2 ), − whereas reactions of V(NSiMe 3 )Cl 3 with PR 3 Cl 2 or Me 3 SiNP(C 2 F 5 ) 2 Cl resulted in the vanadium(V)−phosphinimide complexes V(NPR 3 ) n Cl 5 - n (R = Ph, n = 1−4, R 3 = MePh 2 , Me 2 Ph, n = 1) and VCl 2 (NP(C 2 F 5 ) 2 NP(C 2 F 5 )NP(C 2 F 5 ) 2 ), respectively. − In addition, several groups have reported related vanadium(IV)− and vanadium(III)−phosphinimide derivatives. − In this paper, we describe our efforts to prepare and characterize V(V)−phosphinimide derivatives. A series of vanadium−imide−phosphinimide complexes are reported.…”

Transition and Main Group Metals in Cyclic Phosphazanes and Phosphazenes

“…160 pm, in contrast to H2NPPh2NPPh2NH2+Cl*, where the terminal bonds are longer (ca. 164 pm) and the central bonds are shorter,180* and to Me3SiN==PPh2-N=PPh2-N(SiMe3)2, with alternating short and long bonds. 132 Several resonance structures can be formulated for the unsaturated heterocycles 34-38 exemplarily shown for six-membered rings (one possible resonance form G' is omitted).…”

“…Its structure has been derived from mass and multinuclear magnetic resonance spectroscopy. 164 The other, 36b, has been detected in the mass spectrum of a linear ionic precursor. 168 Similar behavior has been found with intermediates in the formation of several compounds 34.165a N-^\ \ PR 2 N.…”