Crystal structures of the phosphoraneiminato complexes [Ti3IV;Cl8(NPMe3)3]Cl and [V2III/IV;Cl4(NPPh3)3]

[Ti3Cl8(NPMe3)(3)]Cl has been prepared by the reaction of TiCl3 (THF)(3) with Me3SiNPMe3 in dichloromethane forming green moisture sensitive crystals. According to the crystal structure determination the titanium atoms of the cation [Ti3Cl8(NPMe3)(3)](+) are linked by two mu(3)-N atoms of two NPMe3- groups forming a distorted trigonal-bipyramidal arrangement. The third NPMe3- group and two of the chlorine atoms have mu(2)-bridging functions. The mixed-valence complex [V2Cl4(NPPh3)(3)] is formed as dark green moisture sensitive crystals by the reaction of vanadium trichloride with Me3SiNPPh3 in boiling toluene. According to the crystal structure determination the vanadium atoms are linked by two mu(2)-N atoms of two NPPh3- groups forming a nonplanar V2N2 four-membered ring with a V-V distance of 266.8(1) pm which corresponds to a (sigma, 1/2 pi) 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.