Titanium methyl tamed on silica: synthesis of a well-defined pre-catalyst for hydrogenolysis of n-alkane†
Alkylation of Ti(CH3)2Cl2 1 by MeLi gives the homoleptic Ti(CH3)4 2 for the first time in the absence of any coordinating solvent. The reaction of 2 with silica pretreated at 700 °C (SiO2–700) gives two inequivalent silica-supported Ti-methyl species 3. Complex 3 was characterized by IR, microanalysis (ICP-OES, CHNS, and gas quantification), and advanced solid-state NMR spectroscopy (1H, 13C, DQ, TQ, and HETCOR). The catalytic activity of the pre-catalyst 3 is investigated in low-temperature hydrogenolysis of propane and n-butane with TONs of 419 and 578, respectively.