eta(2)-sulfenamido and -selenamido complexes of titanium, zirconium, molybdenum and tungsten

The interaction of TiCl4 with LiN(Bu(t))SR (R = Ph or C(6)H(2)Me(3)-2,4,6) gave the sulfenamido complexes TiCl2(eta(2)-Bu(t)NSR)(2). Interaction of ZrCl4 with 3 equivalents of LiN(Bu(t))SPh produced ZrCl(eta(2)-Bu(t)NSPh)(3) while ZrCl4(tht)(2) (tht = tetrahydrothiophene) with 5 equivalents gave the homoleptic Zr(eta(2)-Bu(t)NSPh)(4). From ZrCl2(eta(5)-C5H5)(2) only ZrCl(eta(5)-C5H5)(2)(eta(2)-Bu(t)NSPh) 5 is obtained. Using as starting materials MO(2)Cl(2)(dme) (dme = 1,2-dimethoxyethane, M = Mo or W), MoCl2(NBu(t))(2) and WCl2(NBu(t))(2)(py)(2) (py = pyridine), interactions with LiNBu(t)SPh gave eta(2)-sulfenamido compounds such as MoO2(eta(2)-Bu(t)NSPh)(2). The selenium analogue of the tungsten compound, i.e. W(NBu(t))(2)(eta(2)-Bu(t)NSePh)(2) has been made by interaction of Li2W(NBu(t))(4) with PhSeBr. Where study was possible, NMR spectra over a temperature range indicate that invertomers and isomers occur. Six compounds have been structurally characterised by X-ray diffraction. In all cases the sulfenamido ligands are eta(2) bonded and the geometry about the N atoms is planar.