A Coordination Network That Catalyzes O 2 -Based Oxidations

作者：Jong Woo Han, Craig L. Hill · 发表于：Journal of the American Chemical Society · 年份：2007 · DOI：10.1021/ja069319v · 被引用次数：269 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Polyoxometalates: Synthesis and Applications、Lanthanide and Transition Metal Complexes

Reaction of Tb(III) and two bridging ligands, a redox-active benzoic acid-terminated hexavandate ([V 6 O 13 {(OCH 2 ) 3 C(4-CONHC 6 H 4 CO 2 H)} 2 ] 2- ( 1 ) and 4,4‘-bis(pyridine- N -dioxide) (bpdo) produces a catalytically active open-framework pillared layer-type coordination polymer, Tb1 . The network material catalyzes aerobic oxidation of PrSH to PrSSPr and the oxidation tetrahydrothiophene (THT) to tetrahydrothiophene oxide (THTO) by tert -butylhydroperoxide under ambient conditions. Tb(III) ions and bpdo units form two-dimensional (2D) coordination layers, and the 2D layers are connected by 1 to produce a three-dimensional coordination network. IR and powder X-ray diffraction of Tb1 before and after catalysis indicate the catalyst maintains an open framework structure during the catalytic reactions.