The free-radical substitution of ferrocene and the stability of ferrocenylmethyl radical.
| dc.contributor.advisor | Beckwith, A. L. J. | en |
| dc.contributor.author | Vickery, G.G | en |
| dc.contributor.school | Department of Organic Chemistry | en |
| dc.date.issued | 1971 | en |
| dc.description.abstract | The electron transfer between ferrocene and triphenylmethyl tetrafluoroborate has been shown to be moderately fast, and to be completely independent of the subsequent substitution of ferrocene. Methyl-, isopropyl-, benzyl-, and phenyl-ferrocene have been mono-benzoylated by free-radical and electrophilic methods. For a particular ferrocene the isomer distributions of the products in both methods have been found to be identical. It was concluded that free-radical substitution of ferrocenium ion and electrophilic substitution of ferrocene pass through a common transition state. Some benzoylferrocenes which are inaccessible by electrophilic substitution may be synthesized by the free-radical route; the synthesis of p-benzoylferrocene in moderate yields was achieved. The reaction of ferrocenium ion with alkyl radicals generated from triorganotin hydrides and alkyl halides was investigated. A value of c.7x10⁵ 1. mol ⁻¹s ⁻¹ at 25°C was derived for the rate constant for ferrocenium ion substitution by alkyl radicals. The stability of ferrocenylmethyl radical has been investigated by studying the products obtained from the one-electron reductions of a series of alkyl (ferrocenylmethyl) quaternary ammonium salts. The stability of this radical is intermediate between that of benzyl and t-butyl radicals. A method of synthesizing ferrocenylmethylamines from ferrocenylmethanol and amines has been explored, and shown to depend upon the pH of the solution, and on the nature of the amine. | en |
| dc.description.dissertation | Thesis (Ph.D.) -- University of Adelaide, Department of Organic Chemistry, 1971 | en |
| dc.identifier.uri | http://hdl.handle.net/2440/77816 | |
| dc.subject | ferrocenium ion, electrophilic substitution | en |
| dc.title | The free-radical substitution of ferrocene and the stability of ferrocenylmethyl radical. | en |
| dc.type | Thesis | en |
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