Insertion Reactions into the Metal−Alkyl and Metal−Amido Bonds of 1,3-Di(silyl-η-amido)cyclopentadienyl Titanium and Zirconium Complexes

The synthesis of the methyl complexes [M{η5-C5H3-1,3-(SiMe2-η-NtBu)2}Me] (M = Ti, Zr)
and the results of the insertion reactions into their metal−methyl bonds have been
investigated and compared with the similar reactions previously reported for related metal−amido [M{η5-C5H3-1,3-(SiMe2-η-NtBu)2}(NMe2)] (M = Ti, Zr) and metal−benzyl [M{η5-C5H3-1,3-(SiMe2-η-NtBu)2}(CH2Ph)] (M = Ti, Zr) compounds. The structural characterization of
the resulting η2-iminocarbamoyl [Zr{η5-C5H3-1,3-(SiMe2-η-NtBu)2}{η2-C(NMe2)N(2,6-Me2C6H3)}], η2-iminoacyl [M{η5-C5H3-1,3-(SiMe2-η-NtBu)2}(η2-CR‘NR)] (M = Zr, R = 2,6-Me2C6H3, R‘ = CH2Ph, Me; M = Zr, R = tBu, R‘ = Me; M = Ti, R = 2,6-Me2C6H3, R‘ = Me),
and alkoxo [Zr{η5-C5H3-1,3-(SiMe2-η-NtBu)2}{OC(CH2Ph)Ph2}] complexes and of the asymmetrical bicyclic enediamido compound [Ti(η5-C5H3-1,3-{(SiMe2-η-NtBu)(SiMe2-NtBu-C(η-NR)C(Me)(η-NR)}] (R = 2,6-Me2C6H3), formed by coupling iminoacyl and iminocarbamoyl
ligands, is also described. The molecular structures of the zirconium complexes [Zr{η5-C5H3-1,3-(SiMe2-η-NtBu)2}Me] and [Zr{η5-C5H3-1,3-(SiMe2-η-NtBu)2}{η2-C(CH2Ph)N(2,6-Me2C6H3)}]and the titanium derivative [Ti(η5-C5H3-1,3-{(SiMe2-η-NtBu)(SiMe2-NtBu-C(η-NR)C(Me)(η-NR)}] (R = 2,6-Me2C6H3) have been determined by X-ray diffraction studies.