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DOI: 10.1055/sos-SD-002-00797

Negishi, E.-i.; Takahashi, T.Science of Synthesis, (20032707.

The reaction of alkyl halides with a bis(η5-cyclopentadienyl)zirconium derivative Zr(Cp)2 has been shown to give products of the type [Zr(Cp)2R1X].[‌127‌] Primary alkyl halides generally give such complexes in good yields, whereas tertiary alkyl halides predominantly or exclusively produce compounds of the type [Zr(Cp)2X2]. With secondary alkyl halides, mixtures of the two kinds of product are obtained.[‌127‌] The reaction has been shown to proceed via radical intermediates. The reaction of allylic and propargylic ethers with dibutylbis(η5-cyclopentadienyl)zirconium(IV) (64) and similar derivatives as Zr(Cp)2 equivalents provides a convenient route to monoallyl- and monoallenylbis(η5-cyclopentadienyl)zirconium derivatives such as 65-69 (Scheme 28).[‌13‌,‌97‌,‌128‌,‌129‌]

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