Oxoaryls of rhenium-(V) and -(VI) and osmium(VI). X-Ray crystal structures of dimesityldioxorhenium(VI), tetramesityloxorhenium(VI), and dimesityldioxoosmium(VI)

Abstract
The interaction of mesitylmagnesium bromide with [Me3NH][ReO4] or Re2O7 leads to the isolation of the diamagnetic rhenium(V) complex [(mes)2ReO2]2Mg(thf)2(mes = mesityl, thf = tetra-hydrofuran), which can be oxidized to the paramagnetic compound ReO2(mes)2; ReOCl4 gives, instead, the paramagnetic rhenium(V) complex ReO(mes)4 along with minor amounts of ReO2(mes)2, upon oxidation of the reaction solutions. All three rhenium starting materials with O-tolylmagnesium bromide or o-methoxyphenylmagnesium bromide lead similarly to the paramagnetic complexes ReO(o-MeC6H4)4 and ReO(o-MeOC6H4)4, respectively. The diamagnetic compound OsO2(mes)2 has also been prepared by oxidizing solutions from the interaction of osmium tetraoxide with the appropriate Grignard reagent. The X-ray crystal structures of ReO2(mes)2, OsO2(mes)2, and ReO(mes)4 have been determined to reveal tetrahedral, tetrahedral, and tetragonal pyramidal geometries respectively.

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