CYCLOTHIAZENO COMPLEXES OF TUNGSTEN WITH PHOSPHORANEIMINATO AND T-BUTOXY LIGANDS

The cyclothiazeno complex [WCl3(N3S2)](2) reacts with the silylated ph osphaneimine Me3SiNPPh3 in THF solution forming the cyclothiazenophosp horaneiminato complex [Cl2W(N3S2)(NPPh3)](n) which forms green crystal s of [Cl2W(N3S2)(Npph(3))(Py)] (1) when pyridine is added. The corresp onding reaction with Me3SiNPMe3 leads to the methyl derivative which i s analogous to 1 and which is obtained as dark green crystals along wi th the tetrakis(phosphoraneiminato) complex of the crystal composition [W(NPMe3)(4)]Cl-2. 2 [Cl2W(N3S2)(NPMe3)(Py)]. 2 CH2Cl2 (2). According to the crystal structure analyses the phosphoraneiminato ligands NPR3 - cause as a result of the short WN bonds of approximately 180 pm a st rong trans influence on one of the WN bonds of the planar WN3S2 rings and alternatingly long SN bonds. With LiOCMe3 [WCl3(N3S2)](2) reacts f orming the centro-symmetrically dimeric cyclothiazeno alkoxy complex [ (Me3CO)(4)W(N3S2)Li2Cl](2) (3) the ion ensemble of which is linked via the lithium and the chlorine atoms.