Tantalum hydrides supported on MCM-41 mesoporous silica : Activation of methane and thermal evolution of the tantalum-methyl species

The Ta(=CHtBu)(CH 2 tBu) 3 complex 1 reacts with the OH groups of a MCM-41 mesoporous silica dehydroxylated at 500 °C to form the monosiloxy surface species [(≡SiO)Ta(=CHtBu)(CH 2 tBu) 2 ] 2, with evolution of 1 equiv per Ta of neopentane. Complex 2 leads to a mixture of supported tantalum hydrides [(≡SiO) 2 Ta(H) x ] (x = 1, 3), 3, by treatment under hydrogen at 150 °C. These surface complexes were characterized by the combined use of several techniques such as IR and EXAFS spectroscopies as well as 1 H MAS, 13 C CP/MAS, 2D 1 H- 13 C HETCOR, and J-resolved solid-state NMR and mass balance analysis. The surface tantalum hydrides evolve reversibly to the monohydride species (≡SiO) 2 Ta-H by heating at 150 °C under vacuum; they lead progressively to the complete formation of the supported trisiloxy tantalum complex (≡SiO) 3 Ta by heating under hydrogen (600 Torr) up to 500 °C. They can activate at 150 °C the C-H bond of CH 4 to form first the surface tantalum methyl species [(≡SiO) 2 Ta-(CH 3 ) x ] with liberation of H 2 . The initially rapid decrease of the v(Ta-H) bands followed by a slower rate indicates the presence of a distribution of Ta-H sites of various reactivity. The combined use of 13 C CP/MAS solid-state NMR and 100% 13 C-labeled methane affords the observation of methylidene and methylidyne species on a few tantalum sites, which indicates the occurrence of an α-H elimination process. In parallel, a progressive transfer of methyl groups from tantalum to neighboring siloxane bridges was also evidenced, which grows with temperature; this process is reasonably accompanied by the formation of the trisiloxy tantalum complex (≡SiO) 3 Ta.