Catalytic properties of the dioxomolybdenum siloxide MoO 2(OSiPh3)2 and its 2,2′-bipyridine adduct MoO2(OSiPh3)2(bpy)

Abstract

The tetrahedral triphenylsiloxy complex MoO2(OSiPh 3)2 (1) and its Lewis base adduct with 2,2′-bipyridine, MoO2(OSiPh3)2(bpy) (2), were prepared and characterised by IR/Raman spectroscopy, and thermogravimetric analysis. Both compounds catalyse the epoxidation of cis-cyclooctene at 55°C using tert-butylhydroperoxide (t-BuOOH) is decane as the oxidant, giving 1,2-epoxycyclooctane as the only product. The best results were obtained in the absence of a co-solvent (other than the decane) or in the presence of 1,2-dichloroethane, while much lower activities were obtained when hexane or acetonitrile were added. With no co-solvent, catalyst 1 (initial activity 272 mol·molMo-1·h-1 for a catalyst:substrate: oxidant molar ratio of 1:100:150) is much more active than 2 (initial activity 12 mol·molMo-1·h -1). The initial reaction rates showed first order dependence with respect to the initial concentration of olefin. With respect to the initial amount of oxidant, the rate order dependence for 1 (1.9) was higher than that for 2 (1.6). The dependence of the initial reaction rate on reaction temperature and initial amount of catalyst was also studied for both catalysts. The lower apparent activation energy of 1 (11 kcal·mol-1) as compared with 2 (20 kcal·mol-1) is in accordance with the higher activity of the former. © 2006 by MDPI.