Hydrothermal Synthesis, Crystal Structure, and Catalytic Potential of a One-Dimensional Molybdenum Oxide/Bipyridinedicarboxylate Hybrid
authors Amarante, TR; Neves, P; Valente, AA; Paz, FAA; Fitch, AN; Pillinger, M; Goncalves, IS
nationality International
journal INORGANIC CHEMISTRY
keywords METAL-ORGANIC FRAMEWORK; STATE COORDINATION CHEMISTRY; TEMPERATURE IONIC LIQUIDS; OLEFIN EPOXIDATION; DIOXOMOLYBDENUM(VI) COMPLEXES; POLYOXOMOLYBDATE CLUSTERS; OCTAMOLYBDATE CLUSTERS; CARBON-DIOXIDE; METHYL OLEATE; ACTIVE-SITES
abstract The reaction of MoO3, 2,2'-bipyridine-5,5-dicarboxylic acid (H(2)bpdc), water, and dimethylformamide in the mole ratio 1:1:1730:130 at 150 degrees C for 3 days in a rotating Teflon-lined digestion bomb leads to the isolation of the molybdenum oxide/bipyridinedicarboxylate hybrid material (DMA)[MoO3(Hbpdc)]center dot nH(2)O (1) (DMA = dimethylammonium). Compound 1 was characterized by scanning electron microscopy, FT-IR and C-13{H-1} CP MAS NMR spectroscopies, and elemental and thermogravimetric analyses. The solid state structure of 1 was solved and refined through Rietveld analysis of high resolution synchrotron X-ray powder diffraction data in conjunction with information derived from the above techniques. The material, crystallizing in the noncentrosymmetric monoclinic space group Pc, is composed of an anionic one-dimensional organic-inorganic hybrid polymer, (1)(infinity)[MoO3(Hbpdc)](-), formed by corner-sharing distorted {MoO4N2} octahedra, which cocrystallizes with charge-balancing DMA(+) cations and one water molecule per metal center. In the crystal structure of 1, the close packing of individual anionic polymers, DMA(+) cations, and water molecules is mediated by a series of supramolecular contacts, namely strong (O-H center dot center dot center dot O, N+-H center dot center dot center dot O-) and weak (C-H center dot center dot center dot O) hydrogen bonding interactions, and pi-pi contacts involving adjacent coordinated Hbpdc(-) ligands. The catalytic potential of 1 was investigated in the epoxidation reactions of the bioderived olefins methyl oleate (Ole) and DL-limonene (Lim) using tert-butylhydroperoxide (TBHP) as the oxygen donor and 1,2-dichloroethane (DCE) or (trifluoromethyl)benzene (BTF) as cosolvent, at 55 or 75 degrees C. Under these conditions, 1 acts as a source of active soluble species, leading to epoxide yields of up to 98% for methyl 9,10-epoxystearate (BTF, 75 degrees C, 100% conversion of Ole) and 89% for 1,2-epoxy-p-menth-8-ene (DCE, 55 degrees C, 95% conversion of Lim). Catalytic systems employing the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide as solvent could be effectively recycled.
publisher AMER CHEMICAL SOC
issn 0020-1669
year published 2013
volume 52
issue 8
beginning page 4618
ending page 4628
digital object identifier (doi) 10.1021/ic400248m
web of science category Chemistry, Inorganic & Nuclear
subject category Chemistry
unique article identifier WOS:000317712000062
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journal impact factor 4.700
5 year journal impact factor 4.513
category normalized journal impact factor percentile 90.000
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