Multiple bonds between main group elements and transition metals, 155. (hexamethylphosphoramide) methyl(oxo) bis(η2-peroxo) rhenium(vii), the first example of an anhydrous rhenium peroxo complex: Crystal structure and catalytic properties

Article abstract of DOI:10.1016/0022-328X(96)06272-9

Methyl(oxo)bis(η²-peroxo)rhenium(VII) 1, the active species of the system CH₃ReO₃/H₂O₂ in the catalytic oxidation of different organic and organometallic compounds, is stabilized by a water molecule attached to the rhenium center. This water molecule can be removed and substituted by hexamethylphosphoramide (HMPA) to yield (hexamethylphosphoramide)methyl(oxo)bis(η²-peroxo)rhenium(VII) (3). The synthesis, crystal structure (X-ray diffraction study), and catalytic properties of which compound are reported. Crystal data are as follows: monoclinic, space group P2₁/n, a = 900.76(7) pm, b = 1229.80(11) pm, c = 1318.57(11) pm, β = 90.251(7)°, R_w = 0.034 for 1878 reflections. The catalytic properties of compound 3 in the oxidation of olefins with H₂O₂ are similar to those of 1.