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DOI: 10.1039/A606644E (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1063-1068

Organoimido complexes of tungsten-(VI) and -(V): correlation between relative orientation of π-donor ligands and electron configuration of the metal

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Lars Wesemann, Ludger Waldmann, Uwe Ruschewitz, Beate Ganter and Trixie Wagner

Abstract

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.

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