Synthesis and Catalytic Properties of Molybdenum(VI) Complexes with Tris(3,5-dimethyl-1-pyrazolyl)methane
authors Neves, P; Gago, S; Balula, SS; Lopes, AD; Valente, AA; Cunha-Silva, L; Paz, FAA; Pillinger, M; Rocha, J; Silva, CM; Goncalves, IS
nationality International
journal INORGANIC CHEMISTRY
keywords BOND-VALENCE PARAMETERS; CRYSTAL-STRUCTURE; TRIS(PYRAZOLYL)METHANE LIGANDS; OLEFIN EPOXIDATION; WATER CLUSTER; FRAMEWORK; COORDINATION; FUNCTIONALITY; CHEMISTRY; NETWORKS
abstract The complex [MoO2Cl{HC(3,5-Me(2)pz)(3)}]BF4 (1) (HC(3,5-Me(2)pz)(3) = tris(3,5-dimethyl-1-pyrazolyl)methane) has been prepared and examined as a catalyst for epoxidation of olefins at 55 degrees C using tert-butyl hydroperoxide (TBHP) as the oxidant. For reaction of cis-cyclooctene, epoxycyclooctane is obtained quantitatively within 5 h when water is rigorously excluded from the reaction mixture. Increasing amounts of water in the reaction mixture lead to lower activities (without affecting product selectivity) and transformation of 1 into the trioxidomolybdenum(VI) complex [{HC(3,5-Me(2)pz)(3)}MoO3] (4). Complex 4 was isolated as a microcrystalline solid by refluxing a suspension of 1 in water. The powder X-ray diffraction pattern of 4 can be indexed in the orthorhombic Pnma system, with a = 16.7349(5) angstrom, b = 13.6380(4) angstrom, and c = 7.8513(3) angstrom. Treatment of 1 in dichloromethane with excess TBHP led to isolation of the symmetrical [Mo2O4(mu(2)-O){HC(3,5-Me(2)pz)(3)}(2)}(BF4)(2) (2) and unsymmetrical [Mo2O3(O-2)(2)(mu(2)-O)(H2O){HC(3,5-Me(2)pz)(3)}] (3) oxido-bridged dimers, which were characterized by single-crystal X-ray diffraction. Complex 2 displays the well-known (Mo2O5)(2+) bridging structure where each dioxidomolybdenum(VI) center is coordinated to three N atoms of the organic ligand and one mu(2)-bridging O atom. The unusual complex 3 comprises dioxido and oxidodiperoxo molybdenum(VI) centers linked by a mu(2)-bridging O atom, with the former center being coordinated to the tridentate N-ligand. The dinuclear complexes exhibit a similar catalytic performance to that found for mononuclear 1. For complexes 1 and 2 use of the ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate and N-butyl-3-methylpyridinium tetrafluoroborate as solvents allowed the complexes to be completely dissolved, and in each case the catalyst and IL could be recycled and reused without loss of activity.
publisher AMER CHEMICAL SOC
issn 0020-1669
year published 2011
volume 50
issue 8
beginning page 3490
ending page 3500
digital object identifier (doi) 10.1021/ic102456z
web of science category Chemistry, Inorganic & Nuclear
subject category Chemistry
unique article identifier WOS:000290457700042
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