American Chemical Society
ja069319v_si_003.pdf (1.79 MB)

A Coordination Network That Catalyzes O2-Based Oxidations

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journal contribution
posted on 2007-12-12, 00:00 authored by Jong Woo Han, Craig L. Hill
Reaction of Tb(III) and two bridging ligands, a redox-active benzoic acid-terminated hexavandate ([V6O13{(OCH2)3C(4-CONHC6H4CO2H)}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.