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Please login to access the full content or check if you have access via Method 7: Formation of Bis(η5-cyclopentadienyl)zirconium(III) Complexes

DOI: 10.1055/sos-SD-002-00797

Negishi, E.-i.; Takahashi, T.Science of Synthesis, (20032793.

This type of complex is relatively rare. Mild reduction of bis(η5-cyclopentadienyl)zirconi­um(IV) or mild oxidation of bis(η5-cyclopentadienyl)zirconium(II) complexes can afford the bis(η5-cyclopentadienyl)zirconium(III) derivatives.[‌193‌,‌354‌,‌356‌] Some examples are shown in Scheme 148. The chloro-bridged complex 406 can be obtained by reaction of dichloro­bis[η5-1,3-bis(trimethylsilyl)cyclopentadienyl]zirconium(IV) with sodium/mercury amalgam.[‌354‌] When bis(η5-cyclopentadienyl)diiodozirconium(IV) is treated with tert-butyllithium at low temperature, tetrakis(η5-cyclopentadienyl)di-μ-iododizirconium(III) (407) is obtained as a poorly soluble complex via bis(η5-cyclopentadienyl)iodo(isobutyl)zirconi­um(IV).[‌356‌] Zirconocene derivatives with alkyl-substituted cyclopentadienyl ligands are relatively stable and photolysis is required for the formation of 409 from iodo(isobutyl)­bis(η5-methylcyclopentadienyl)zirconium(IV) (408).[‌356‌]

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