| Abstract |
The dioxomolybdenum and dioxotungsten complexes [MoO2L1] (1-Mo) and [WO2L1] (2-W), supported by a diamine bis(phenolate) ligand (L-1= Me2NCH2CH2N(CH2-2-O-3,5-(C6H2Bu2)-Bu-t)(2)) were prepared from MoO2Cl2 and WO2Cl2(dme) in good yields. The solid-state structures of both compounds obtained by single crystal X-ray diffraction reveal distorted octahedral geometries around the metals with cis terminal oxo ligands. Their performance in the catalytic epoxidation of cis-cyclooctene using H2O2 and TBHP as oxidants was evaluated. 2-W displays high activity with H2O2 as terminal oxidant, achieving 84\% conversion in 6 h (TOF = 1400 mol(sub)mol(cat)(-1)h(-1)), while its molybdenum counterpart 1-Mo was inactive in the same conditions. Using TBHP as oxidant the opposite trend was observed and 1-Mo attained 93\% conversion in 6 h (TOF = 1550 mol(sub)mol(cat)(-1)h(-1)). The Oxovanadium complexes [(VOLCl)-Cl-1] (3-V), [(VOLCl)-Cl-2] (4-V, L-2 = Me2NCH2CH(CH3)N(CH2-2-O-3,5-(C6H2Bu2)-Bu-t)(2)) and [(VOL1)(2)(mu-O)] (5-V) were also tested as catalysts in the epoxidation of cis-cyclooctene. The three compounds display high activity when the epoxidation reaction is performed using TBHP as oxidant. Using H2O2, 3-V and 4-V are moderately active while 5-V is inactive. (C) 2011 Elsevier B. V. All rights reserved. |
