Novel vanadium(III) complexes with rigid phenylpolycarboxylate ligands: Synthesis, structures and application in C-H bond activation

摘要

Two novel vanadium(iii) complexes: V(dipic)(Hbdc)(H_2O) _2 (1) and [V_2(dipic)_2(H_2btec)(H _2O)_4]·2H_2O (2) (H_2dipic = 2,6-pyridinedicarboxylic acid, H_2bdc = 1,3-benzene-dicarboxylic acid, H_4btec = 1,2,4,5-benzenetetracarboxylic acid) are synthesized by the reaction of V_2(SO_4)_3, 2,6-pyridinedicarboxylic acid and 1,3-benzene-dicarboxylic acid (for 1) or 1,2,4,5- benzenetetracarboxylic acid (for 2) under hydrothermal condition at 120 °C for 3 days. They were characterized by elemental analysis, IR, UV-Vis, single crystal X-ray diffraction analysis and thermogravimetric analyses (TG). Structural analyses show that the vanadium atoms in the complexes 1 and 2 are both in a pentagonal-bipyramidal coordination environment with the NO6 donor set, and there is intermolecular hydrogen bonding in each complex. Research results found that the complexes exhibited bromination catalytic activity in the single-pot reaction of the conversion of phenol red to bromophenol blue in the mixed solution of H_2O-DMF at the constant temperature of 30 ± 0.5 °C with pH = 5.8, and catalytic C-H bond cleavage activity for the peroxidative oxidation (with hydrogen peroxide) of cyclohexane to cyclohexanol and cyclohexanone (the maximum total turnover number is 395) under the mild conditions.