Die Kristallstruckturen der Phosphaniminato-Komplexe.[Ti₃ ^IVCl₈(NPMe₃)₃]Cl und [V₂ ^III/IVCl₄(NPPh₃)₃]/Crystal Structures of the Phosphoraneiminato Complexes [Ti₃ ^IVCl₈(NPMe₃)₃]Cl and [V₂ ^III/IVCl₄(NPPh₃)₃]

Abstract

Abstract [Ti 3 Cl 8 (NPMe 3 ) 3 ]Cl has been prepared by the reaction of TiCl 3 (THF) 3 with Me 3 SiNPMe 3 in dichloromethane forming green moisture sensitive crystals. According to the crystal structure determination the titanium atoms of the cation [Ti 3 Cl 8 (NPMe 3 ) 3 ] + are linked by two μ 3 -N atoms of two NPMe 3 - groups forming a distorted trigonal-bipyramidal arrangement. The third NPMe 3 - group and two of the chlorine atoms have μ2-bridging functions. The mixed-valence complex [V 2 Cl 4 (NPPh 3 ) 3 ] is formed as dark green moisture sensitive crystals by the reaction of vanadium trichloride with Me 3 SiNPPh 3 in boiling toluene. According to the crystal structure determination the vanadium atoms are linked by two μ 2 -N atoms of two NPPh 3 - groups forming a nonplanar V 2 N 2 four-membered ring with a V-V distance of 266.8(1) pm which corresponds to a (σ, 1/2π) bond type. This is confirmed by the measurement of the magnetic susceptibility which leads to a magnetic moment of 1.45(5) B. M., corresponding to the remaining d 1 -electron.