Date of Award

2-1989

Document Type

Dissertation - Restricted

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Willam A. Donaldson

Second Advisor

Sheldon E. Cremer

Third Advisor

Albert W. Jache

Fourth Advisor

Michael A. McKinney

Fifth Advisor

E. Alexander Hill

Abstract

Several (1-substituted-pentadienyl)iron(+1) complexes were synthesized (II-8a R = Me, II-8b R = Et, II-8c R = Pr, II-8d R = Bu, II-8e R = pentyl, II-8f R = hexyl, II-8g R = heptyl, II-8j R = Ph, II-8k R = COOMe, and II-8l R = COOEt). The reaction of II-8a, II-8b, II-8c, II-8j, II-8k, and II-8l was investigated. The reaction of II-8a, II-8b, II-8c, and II-8j gave (diene)iron compounds due to attack at the dienyl terminal carbons. Depending on the nature of the substituent, either cis(diene)iron and/or cis,trans(diene)iron products were obtained. The ratio of these regiomers depends on the nature of the substituent on the cation. (1-alkyl-pentadienyl)iron(+1) cations, II-8a ... II-8c gave a mixture of cis(diene)iron and cis,trans(diene)iron and cis,trans(diene)iron complexes. (1-phenyl-pentadienyl)iron(+1) cation gave cis(diene)iron products. It appears that the nucleophilic attack to II-8a, II-8b, II-8c and II-8j is under overall frontier orbital control. Surprisingly when (pentadienyl)iron(+1) cation II-8k and II-8l were reacted with lithio dimethylmalonate gave $\pi$-$\sigma$-allyl complexes III-68, and III-69 respectively from nucleophilic attack at the internal dienyl carbon (C2) due to charge control. Decomplexation of III-68 and III-69 with Ce(NH$\sb4)\sb2$(NO$\sb3)\sb6$ gave trisubstituted cyclopropane carboxylates III-77 and III-78 respectively. Unlike the malonate anion, the reaction of lithio phenylacetylene with the cations II-8a and II-8k gave only decomposed products. The reaction of dilithio -tris(phenylethynyl)cuprate and dilithio tris(heptynyl)cuprate with (pentadienyl)iron(+1) cations, II-8a, II-8j and II-8k gave only (E,Z-dienyne)iron complexes (III-80, III-81, III-82, and III-83) due to attack at the unsubstituted dienyl terminal carbon. The alkynylcuprates addition to (pentadienyl)iron(+1) cations is under overall frontier orbital control. The reaction of trimethylsilylphenylacetylene and trimethylsilylheptyne with (1-methoxycarbonyl-pentadienyl) cation, II-8k gave only (E,E-dienyne)iron complexes (III-84 and III-85) respectively.

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