Lars Wesemann, Ludger Waldmann, Uwe Ruschewitz, Beate Ganter and Trixie Wagner
The high-yield synthesis of the monomeric five-co-ordinate arylimido complex [WCl3(NPh)(OC6H3Pri2 -2,6)] was achieved starting from [{WCl3(NPh)}2(µ-Cl)2]. The adducts [WCl3(NPh)(OC6H3Pri2 -2,6)L] (L = tetrahydrofuran, pyridine (py) or 4-tert-butylpyridine) of the monoalkoxide have been synthesized and the constitution of the pyridine adduct determined by X-ray crystallography. The reduction of the monoalkoxide with 1 equivalent of sodium amalgam in the presence of pyridine or triethylphosphine leads to the paramagnetic adducts [WCl2(NPh)(OC6H3Pri2 -2,6)L2] (L = py or PEt3) which were characterized. A trans configuration was found for the two chlorine atoms and the two σ-donor ligands in the structure analysis. Reorganization of the two π-donor ligands (aryloxide and NPh) from a cis arrangement in the complex with d0 electron configuration to a trans arrangement in the d1 configurated complexes is found and verified by X-ray diffraction analyses.