Abstract
The three Cp*W(NO)(η1-isonitrile)2 complexes [Cp* = η5-C5Me5; isonitrile = CNCMe3 (1), CN-2,6-Me2C6H3 (2), CN-n-C4H9 (3)] possess asymmetrical “piano-stool” molecular structures in the solid state in which their two isonitrile ligands exhibit distinctly different degrees of W→isonitrile back-bonding. Thus, an X-ray crystallographic analysis of 1 as a benzene hemisolvate has established that it has one essentially linear isonitrile ligand having a C−N bond length of 1.159(5) A and a C−N−C bond angle of 171.4(5)° and one very bent isonitrile ligand (indicative of considerable W→CNCMe3 π-back-bonding) having C−N = 1.200(5) A and C−N−C = 135.1(4)°. Complex 2 crystallizes with two crystallographically independent molecules in the asymmetric unit, and the isonitrile ligands in each of these molecules exhibit metrical parameters similar to those extant in 1. The presence of the inequivalent isonitrile ligands is also manifested in the IR spectra of the three compounds both in the solid state and in solution. For...
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