Phenylimido complexes of tungsten(VI) and tungsten(V). The crystal and molecular structure of Trichloro(phenylimido)bis(trimethylphosphine)tungsten(V)

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Abstract
Tetrachloro(phenylimido)tungsten(VI) is reduced by trimethylphosphine in tetrahydrofuran solution to give the tungsten(V) complex PhNWCl3(Pme3)2 in which the phenylimido multiple bond remains intact. The complex reacts with oxygen to form the phosphine oxide complex PhNWCl3 (OPMe3)2. Pyridine and alkyl cyanides do not reduce tetrachloro(phenylimido)tungsten(V1) but give the adducts PhNWCl4.L (L = py, MeCN, EtCN). The crystal and molecular structure of the title complex has been determined from single-crystal X-ray diffractometer data. The crystals are monoclinic with a 14.903, b 10.221, c 14.380Š β 116.05�, space group P21/c, Z 4. The structure has been solved by Patterson and Fourier methods and refined to R 0.030 for the 1566 observed data. Distorted octahedral coordination geometry is found with two trans trimethylphosphine and two trans chloride ligands; a third chloride is trans to the phenylimido group. The W-N(imido) bond length is 1.731 �.

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