Abstract
Hexadentate chelated trans-1,2-cyclohexanediaminetetraacetato titanate(IV) was used as a model of the Ti(IV) species in the constrained environment of TS-1 (H4cdta=trans-1,2-cyclohexanediaminetetraacetic acid, C14H22O8N2; TS, titanium silicalite). Several complexes were isolated and well characterized, including [Ti(cdta)(H2O)]·2H2O (1), Na2[Ti(O2)(cdta)]·2H2O (2) and (NH4)2[TiO(cdta)]·1.5H2O (3). Octadentate cdta peroxo titanate(IV) (2) is obtained quantitatively from the reaction of the hydrated titanium cdta complex 1 with hydrogen peroxide. The bond distances between O–O and Ti–(O2) are 1.464(3) and 1.908(2)Å, respectively. Transformation of the peroxo titanium(IV) complex with excess H4cdta and heating results in the formation of an interesting oxotitanate in H2O–H2O2 solution. The catalytic activity of 2 was studied for phenol hydroxylation using 30% H2O2, and this was monitored by 1H and 13C NMR techniques. The main product of the reaction is catechol.
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