The reaction of [Ta(=CHtBu)(CH2tBu)3] or [Cp*Ta(CH3)4] with a silica partially dehydroxylated at 700 °C gives the corresponding monosiloxy surface complexes [(≡SiO)Ta(=CHtBu)(CH2tBu)2] and [(≡SiO) Ta(CH3)3Cp*] by eliminating a σ-bonded ligand as the corresponding alkane (H-CH2tBu or H-CH3). EXAFS data show that an adjacent siloxane bridge of the surface plays the role of an extra surface ligand, which most likely stabilizes these complexes as in [(≡SiO)Ta(=CHtBu)(CH2tBu)2(≡SiOSi≡)] (1a′) and [(≡SiO)Ta(CH3)3 Cp*(≡SiOSi≡)] (2a′). In the case of [(≡SiO)Ta(=CHtBu) (CH2tBu)2(≡SiOSi≡)], the structure is further stabilized by an additional interaction: a C-H agostic bond as evidenced by the small J coupling constant for the carbenic C-H (JC-H = 80 Hz), which was measured by J-resolved 2D solid-state NMR spectroscopy. The product selectivity in propane metathesis in the presence of [(≡SiO)Ta(=CHtBu)- (CH2tBU)2(≡SiOSi≡)] (1a′) as a catalyst precursor and the inactivity of the surface complex [(≡SiO)Ta-(CH 3)3CP*(≡SiOSi≡)] (2a′) show that the active site is required to be highly electrophilic and probably involves a metallacyclobutane intermediate.
|Original language||English (US)|
|Number of pages||9|
|Journal||Journal of the American Chemical Society|
|State||Published - Oct 20 2004|
ASJC Scopus subject areas
- Colloid and Surface Chemistry