Thermolabile Organotitanium Monoalkyl Phosphates: Synthesis, Structures, and Utility as Epoxidation Catalysts and...

The reaction of [Cp*TiCl₃] (Cp* = C₅Me₅) with monoalkyl phosphates (RO)PO₃H₂ (R = Me, Et, and ⁱPr) in tetrahydrofuran (THF) at 25 °C leads to the formation of binuclear complexes [Cp*₂Ti₂(μ-O₂P(OH)OR)₂(μ-O₂P(O)OR)₂] [R = Me (1), Et (2), and ⁱPr (3)]. On the other hand, the reaction of ( ^tBuO)₂PO₂K with [Cp*TiCl₃] in acetonitrile or THF results in isolation of either the dinuclear [Cp*₂Ti₂(μ-O₂P(OH)O ^tBu)₂(μ-O₂P(O)O ^tBu)₂] (4) or the trinuclear titanophosphate [Cp*₃Ti₃(μ-O₃PO ^tBu)₂(μ-O)₂(μ-O₂P(O ^tBu)₂)] (5), respectively. The formation of compounds 4 and 5 is facilitated by partial hydrolysis of the tert-butoxy groups of ( ^tBuO)₂PO₂K. New titanophosphates 1-5 have been characterized by spectroscopic and analytical methods, and the molecular structures have further been confirmed by single-crystal X-ray diffraction studies. Thermal decomposition studies of 1-5 reveal the initial loss of thermally labile alkyl substituents of the organophosphate ligands, followed by the loss of C₅Me₅ groups to form an organic-free amorphous titanophosphate in the temperature range 300-500 °C. This material transforms to highly crystalline titanium pyrophosphate TiP₂O₇ at 800 °C. Compounds 1-5 and the TiP₂O₇ materials obtained at 300, 500, and 800 °C through the thermal decomposition of 3 have been employed as efficient homogeneous catalysts for the alkene epoxidation reaction. Using hydrogen peroxide as the oxidant in an acetonitrile medium, these catalysts exhibit >90% alkene conversion with >90% epoxide selectivity in 4 h at temperatures below 100 °C.