Insertion reactions involving a triamidoamine-supported zirconium complex.

The reactivity of a triamidoamine-supported zirconium complex, [κ(5)-N,N,N,N,C-(Me(3)SiNCH(2)CH(2))(2)NCH(2)CH(2)NSiMe(2)CH(2)]Zr (1), toward polar, small-molecule substrates including isocyanides, organic azides, carbodiimides, nitriles, and ketones has been explored. The small-molecule substrates were found to react with the Zr-C bond of complex 1 via 1,1- or 1,2-insertion modes, affording ring-expanded products containing new zirconium-carbon, zirconium-nitrogen, or zirconium-oxygen bonds. Solid-state structures of a 1,1-insertion product [κ(6)-N,N,N,N,N,N-(Me(3)SiNCH(2)CH(2))(2)NCH(2)CH(2)NSiMe(2)CH(2)N(N=NCH(2)Ph)]Zr (3) and a 1,2-insertion product [κ(5)-N,N,N,N,O-(Me(3)SiNCH(2)CH(2))(2)NCH(2)CH(2)NSiMe(2)CH(2)CPh(2)O]Zr (5) are reported.