Crystal Structure and Catalytic Behavior in Olefin Epoxidation of a One-Dimensional Tungsten Oxide/Bipyridine Hybrid

The tungsten oxide/2,2′-bipyridine hybrid material [WO₃(2,2′-bpy)]·nH₂O (n = 1–2) (1) has been prepared in near quantitative yield by the reaction of H₂WO₄, 2,2′-bpy, and H₂O in the mole ratio of ca. 1:2:700 at 160 °C for 98 h in a rotating Teflon-lined digestion bomb. The solid-state structure of 1 was solved and refined through Rietveld analysis of high-resolution synchrotron X-ray diffraction data collected for the microcrystalline powder. The material, crystallizing in the orthorhombic space group Iba2, is composed of a one-dimensional organic–inorganic hybrid polymer, _∞¹[WO₃(2,2′-bpy)], topologically identical to that found in the previously reported anhydrous phases [MO₃(2,2′-bpy)] (M = Mo, W). While in the latter the N,N′-chelated 2,2′-bpy ligands of adjacent corner-shared {MO₄N₂} octahedra are positioned on the same side of the 1D chain, in 1 the 2,2′-bpy ligands alternate above and below the chain. The catalytic behavior of compound 1 for the epoxidation of cis-cyclooctene was compared with that for several other tungsten- or molybdenum-based (pre)­catalysts, including the hybrid polymer [MoO₃(2,2′-bpy)]. While the latter exhibits superior performance when tert-butyl hydroperoxide (TBHP) is used as the oxidant, compound 1 is superior when aqueous hydrogen peroxide is used, allowing near-quantitative conversion of the olefin to the epoxide. With H₂O₂, compounds 1 and [MoO₃(2,2′-bpy)] act as sources of soluble active species, namely, the oxodiperoxo complex [MO­(O₂)₂(2,2′-bpy)], which is formed in situ. Compounds 1 and [WO­(O₂)₂(2,2′-bpy)] (2) were further tested in the epoxidation of cyclododecene, trans-2-octene, 1-octene, (R)-limonene, and styrene. The structure of 2 was determined by single-crystal X-ray diffraction and found to be isotypical with the molybdenum analogue.