Reactions of Aminobis(phenolate)‐Supported Dioxidotungsten(VI) and Dioxidomolybdenum(VI) Complexes

The dioxidotungsten(VI) and ‐molybdenum(VI) complexes [WO2(O2NOMe)] (1), [MoO2(O2NOMe)] (2) and [{MoO2(O2NMe)}2] (3) [O2NOMe methoxyethylamino‐N,N‐bis(2‐methylene‐4,6‐dimethylphenolate) dianion, O2NMe = methylamino‐N,N‐bis(2‐methylene‐4,6‐dimethylphenolate) dianion] can react with chloride sources (Me3SiCl, SOCl2) to form resultant monooxido dichloro compounds [WOCl2(O2NOMe)] (4), [MoOCl2(O2NOMe)] (5) and [MoOCl2(O2NMe)] (6), respectively. The reaction of tungsten complex yields of the mixture of cis‐4 and trans‐4, which can be separated and characterized. The reactions of analogous molybdenum complexes with Me3SiCl yield trans isomers of 5 and 6 as individual products. Reaction of dioxidotungsten complex 1 with isopropyl isocyanate was found to produce a tungsten(VI) complex [W(O2NOMe)(N‐iPr)(L)] (7) (L = N,N′‐diisopropylureate) with a terminal imido group and a bidentate ureate ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)