Functionally Substituted Cyclopentadienyl Metal Compounds

David W. Macomber, William P. Hart, Marvin D. Rausch

Research output: Contribution to journalArticle

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Abstract

The birth of cyclopentadienyl transition-metal chemistry occurred in 1951 when Pauson and Kealy discovered bis(η5–cyclopentadienyl)iron (ferrocene). Sodium cyclopentadienides containing aldehyde, ketone, or ester substituents can be synthesized easily following a method developed originally by Thiele in 1900. Peters has shown that a reaction between equimolar amounts of methyl chloroformate and sodium cyclopentadienide gave two main products. Cyclopentadienide anions possessing electron-withdrawing groups generally have greater air stability than do the corresponding unsubstituted cyclopentadienide anions. Excluding ferrocene and cymantrene, which can be halogenated indirectly via electrophilic substitution, there are two methods available for the synthesis of halocyclopentadienylmetal compounds. Wulfsberg and West have synthesized thallium pentachlorocyclopentadienide as well as other M+C5Cl5 salts and have studied their properties. In 1900, Thiele obtained the first cyclopentadienylmetal compound––sodium nitrocyclopentadienide––from a reaction between cyclopentadiene and ethyl nitrate in the presence of sodium ethoxide.Various nucleophiles reacted with 6-diene to give, after hydrolysis, substituted cyclopentadienes. Schlenk and Bergmann first observed sodium isopropenylcyclopentadienide as the product of a reaction between 6,6-dimethylfulvene and triphenylmethylsodium. Polymer-supported cyclopentadienyl compounds have been synthesized mainly for possible catalytic applications. In general, polystyrene–divinylbenzene copolymers have been used as the polymer supports.

Original languageEnglish (US)
Pages (from-to)1-55
Number of pages55
JournalAdvances in Organometallic Chemistry
Volume21
Issue numberC
DOIs
StatePublished - Jan 1 1982

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Cyclopentanes
Metals
Sodium
Anions
Polymers
Nucleophiles
Thallium
Ketones
Aldehydes
Transition metals
Hydrolysis
Esters
Substitution reactions
Iron
Copolymers
Salts
Electrons
Air
ferrocene
ethyl nitrate

Cite this

Functionally Substituted Cyclopentadienyl Metal Compounds. / Macomber, David W.; Hart, William P.; Rausch, Marvin D.

In: Advances in Organometallic Chemistry, Vol. 21, No. C, 01.01.1982, p. 1-55.

Research output: Contribution to journalArticle

Macomber, David W. ; Hart, William P. ; Rausch, Marvin D. / Functionally Substituted Cyclopentadienyl Metal Compounds. In: Advances in Organometallic Chemistry. 1982 ; Vol. 21, No. C. pp. 1-55.
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