Evidence for Silica Surface Three- and Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts

The single-site silica-supported group IV metal amido complex [Ti­(NMe2)4] gives the tris­(amido)-supported fragment [(Si–O−)­Ti­(−NMe2)3], which transforms into a three-membered metallacycle (called a metallaaziridine) by an α-H transfer between two amido ligands. When the three-membered metallacycle reacts with 1-octene, it gives a five-membered metallacycle by insertion of the double bond into the M–C bond of the metallaziridine. These two metallacycles, key intermediates in the catalytic cycle of the hydroaminoalkylation of terminal olefins, were isolated and fully characterized following the surface organometallic chemistry (SOMC) concept and procedures. This paper shows that surface organometallic chemistry can be used to identify and fully characterize three- and five-membered metallacycles of Ti in the hydroaminoalkylation of olefins.