LAUSR

We report here the preparation and characterization of new well‐defined silica‐supported Ti imido complexes that present an L‐ligand variation in a structure of currently the most active oxo/imido heterometathesis catalyst (≡SiO)Ti(=NtBu)(Me2Pyr)(py)2 (1s), where py is replaced with stronger electron‐donating 4‐(N,N‐dimethylamino)pyridine (2s) or bidentate 2,2′‐bipyridine (3s). The materials were characterized with elemental and mass balance analyses and IR and solid‐state NMR that confirmed the selective formation of surface Ti species with terminal imido ligand. Evaluation of the catalytic oxo/imido heterometathesis activity of the obtained materials demonstrated that L‐ligands have a pronounced influence on the catalytic performance. In particular, the replacement of pyridine with stronger donating ligands resulted in a significant drop of activity. The catalytic results are discussed in view of the reaction mechanism and implications for further catalyst development.