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2.11.5 Product Subclass 5: Five-Membered Metallocycle–Bis(η5-cyclopentadienyl) Derivatives of ­Oxidation State Four

DOI: 10.1055/sos-SD-002-00797

Negishi, E.-i.; Takahashi, T.Science of Synthesis, (20032739.

Five-membered zirconocene and hafnocene derivatives formally belong in Section 2.11.4. Due to their special scientific and synthetic significance, however, these compounds and their three-membered counterparts are separately classified. The latter compounds are often considered as η2-complexes of bis(η5-cyclopentadienyl)zirconium(II) and -hafni­um(II) and they are discussed in Section 2.11.8. Five-membered zirconocene and hafnocene derivatives such as metallacyclopentanes, metallacyclopentenes, and metallacyclopentadienes may contain one or more heteroatoms in the ring moiety (Scheme 74). Five-membered zirconacycles are frequently found as intermediates in bis(η5-cyclopentadi­enyl)zirconium(II)-catalyzed CC bond forming reactions; the catalytic reactions of zirconium(II) complexes are discussed in Section 2.11.8.

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