Synthesis and characterization of η5-cyclopentadienyl–silylallyl niobium and tantalum complexes

Reaction of the disilylcyclopentadiene 1,1-[SiMe2(CH2CHdouble bond; length as m-dashCH2)]2C5H4 with NbCl5 gave the new allylsilyl-substituted monocyclopentadienyl niobium complex [Nb{η5-C5H4SiMe2(CH2CHdouble bond; length as m-dashCH2)}Cl4]. This compound was reacted with LiNHtBu or NH2tBu to give the imido derivative [Nb{η5-C5H4SiMe2(CH2CHdouble bond; length as m-dashCH2)}(NtBu)Cl2], which was further alkylated to the imido alkyl complexes [Nb{η5-C5H4SiMe2(CH2CHdouble bond; length as m-dashCH2)}(NtBu)R2] (R = Me, CH2Ph) and [Nb{η5-C5H4SiMe2(CH2CHdouble bond; length as m-dashCH2)}(NtBu)Cl (CH2Ph)]. Reaction of the imido complexes with the corresponding lithium cyclopentadienides gave the dicyclopentadienyl-imido complexes [M(η5-C5R5){η5-C5H4SiMe2(CH2CHdouble bond; length as m-dashCH2)}(NtBu)Cl] (M = Nb, Ta; R = H, Me). Metallocene dichlorides [M(η5-C5R5){η5-C5H4SiMe2(CH2CHdouble bond; length as m-dashCH2)}Cl2] (M = Nb, Ta; R = H, Me) were easily prepared by reduction with Na/Hg and simultaneous transmetallation of [Ta(η5-C5R5)Cl4] with Li[C5H4SiMe2(CH2CHdouble bond; length as m-dashCH2)] and of [Nb{η5-C5H4SiMe2(CH2CHdouble bond; length as m-dashCH2)}Cl4] with Li(C5R5). All of the new compounds have been characterized by elemental analysis, and IR and NMR spectroscopy.