The spectroscopic characterization of tungsten(V) complexes of the type Cp 2W 2(μ-S) 2EE′. Crystal and molecular structure of Cp 2W 2(μ-S) 2(NSiMe 3) 2

Abstract

The binuclear, sulfur-bridged tungsten complexes Cp 2W 2(μ-S) 2E 2 (ENSiMe 3 ( 1), O ( 2) and S ( 3)) and Cp 2W 2(μ-S) 2EE′ (ENSiMe 3, E′=O ( 4); E NSiMe 3, E′S ( 5); EO, E′S ( 6)) were obtained in low yields from the reactions of bis(trimethylsilyl)sulfur diimide, S(NSiMe 3) 2, with cyclopentadienyl tungsten compounds such as CpW(CO) 3Cl and [CpW(CO) 3] 2. The molecular stereochemistry of 1 was determined by a three-dimensional X-ray diffraction study. The centrosymmetric molecules of 1 contain a planar W 2(μ-S) 2 ring (W-W 2.903(3) Å, S···S 3.651(7) Å, angle WSW 77.0(1)°) and terminal 4-electron imido ligands N(SiMe 3) (angle WNSi 170.9(25)°). Complexes 1–6 were characterized by their IR, 1H and 13C NMR and mass spectra.