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{eta(5)-C5H3-1,3-(SiMe2-eta-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{eta(5)-C5H3-1,3-(SiMe2-eta-NtBu)(2)}(NMe2)] (M = Ti, Zr) and metal-benzyl [M{eta(5)-C5H3-1,3-(SiMe2-eta-NtBu)(2)}(CH2Ph)] (M = Ti, Zr) compounds. The structural characterization of the resulting eta(2)-iminocarbamoyl [Zr{eta(5)-C5H3-1,3-(SiMe2-eta-NtBu)(2)}{eta(2)-C(NMe2)=N(2,6-Me2C6H3)}], eta(2)-iminoacyl [M{eta(5)-C5H3-1,3-(SiMe2-eta-NtBu)(2)}(eta(2)-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{eta(5)-C5H3-1,3-(SiMe2-eta-NtBu)(2)}{OC(CH2Ph)Ph-2}] complexes and of the asymmetrical bicyclic enediamido compound [Ti(eta(5)-C5H3-1,3-{(SiMe2-eta-NtBu)(SiMe2-NtBu-C(eta-NR)=C(Me)(eta-NR)}] (R = 2,6-Me2C6H3), formed by coupling iminoacyl and iminocarbamoyl ligands, is also described. The molecular structures of the zirconium complexes [Zr{eta(5)-C5H3-1,3-(SiMe2-eta-NtBu)(2)}Me] and [Zr{eta(5)-C5H3-1,3-(SiMe2-eta-NtBu)(2)}{eta(2)-C(CH2Ph)=N(2,6-Me2C6H3)}] and the titanium derivative [Ti(eta(5)-C5H3-1,3-{(SiMe2-eta-NtBu)(SiMe2-NtBu-C(eta-NR)=C(Me)(eta-NR)}] (R = 2,6-Me2C6H3) have been determined by X-ray diffraction studies.