Synthesis, Structural Elucidation, and Application of a Pyrazolylpyridine–Molybdenum Oxide Composite as a Heterogeneous Catalyst for Olefin Epoxidation
2012-08-06T00:00:00Z (GMT) by
The reaction of [MoO2Cl2(pypzEA)] (1) (pypzEA = ethyl[3-(pyridin-2-yl)-1H-pyrazol-1-yl]acetate) with water in a Teflon-lined stainless steel autoclave (100 °C) or in an open reflux system leads to the isolation of the molybdenum oxide/pyrazolylpyridine composite material [Mo2O6(HpypzA)] (2; HpypzA = [3-(pyridinium-2-yl)-1H-pyrazol-1-yl]acetate). The solid state structure of 2 was solved through single crystal and powder X-ray diffraction analyses in conjunction with information derived from FT-IR and 13C CP MAS NMR spectroscopies and elemental analyses. In the asymmetric unit of 2, two crystallographically distinct Mo6+ centers are bridged by a syn,syn-carboxylate group of HpypzA. The periodic repetition of these units along the a axis of the unit cell leads to the formation of a one-dimensional composite polymer, ∞1[Mo2O6(HpypzA)]. The outstretched pyrazolylpyridine groups of adjacent polymers interdigitate to form a zipper-like motif, generating strong onset π–π contacts between adjacent rings of coordinated HpypzA molecules. The composite oxide 2 is a stable heterogeneous catalyst for liquid-phase olefin epoxidation.