Abstract
The monoalkyl complexes [Zr{Me~2~Si(η^5^‐C~5~Me~4~)(η^5^‐C~5~H~3~R)}(R′)Cl] [R = Me, R′ = CH~2~Ph (1); R = Me, R′ = CH~2~SiMe~3~ (2); R = __i__Pr, R′ = CH~2~Ph (3); R = __i__Pr, R′ = CH~2~SiMe~3~ (4); R = SiMe~3~, R′ = CH~2~Ph (5); R = SiMe~3~, R′ = CH~2~SiMe~3~ (6)] have been synthesized by the reaction of the corresponding ansa‐metallocene dichloride complex and 1 equiv of the alkyl Grignard reagent. Dialkyl complexes with large alkyl groups only formed for the zirconocene complex containing the ansa ligand Me~2~Si(η^5^‐C~5~Me~4~)(η^5^‐C~5~H~4~) and with the benzyl substituent giving [Zr{Me~2~Si(η^5^‐C~5~Me~4~)(η^5^‐C~5~H~4~)}(CH~2~Ph)~2~] (7). When the alkyl substituent is CH~2~SiMe~3~ only the monoalkyl derivative, [Zr{Me~2~Si(η^5^‐C~5~Me~4~)(η^5^‐C~5~H~4~)}(CH~2~SiMe~3~)Cl] (8), was formed. The insertion reaction of the isocyanide reagent CNC~6~H~3~Me~2~‐2,6 into the zirconium−carbon σ‐bond of complexes 1−8 gave the corresponding η^2^‐iminoacyl compound [Zr{Me~2~Si(η^5^‐C~5~Me~4~)(η^5^‐C~5~H~3~R)}{η^2^‐R′C=NC~6~H~3~Me~2~‐2,6}Cl] [R = Me, R′ = CH~2~Ph (9); R = Me, R′ = CH~2~SiMe~3~ (10); R = __i__Pr, R′ = CH~2~Ph (11); R = __i__Pr, R′ = CH~2~SiMe~3~ (12); R = SiMe~3~, R′ = CH~2~Ph (13); R = SiMe~3~, R′ = CH~2~SiMe~3~ (14); R = H, R′ = CH~2~SiMe~3~ (16)] and [Zr{Me~2~Si(η^5^‐C~5~Me~4~)(η^5^‐C~5~H~4~)}{η^2^‐PhCH~2~C=NC~6~H~3~Me~2~‐2,6}(CH~2~Ph)] (15). The molecular structure of 1 has been determined by single‐crystal X‐ray diffraction studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)