It has been shown that $\eta\sp5$-cyclopentadienyl)dicarbonylcobalt is reactive to Friedel-Crafts' acylation with both organic and organometallic acid chlorides: acetyl, p-anisoyl, benzoyl, 2-naphthoyl, and p-toluoyl chlorides and ($\eta\sp5$-chloroformylcyclopentadienyl)($\eta \sp5$-cyclopentadienyl)iron, bis($\eta\sp5$-chloroformylcyclopentadienyl)iron, and ($\eta\sp5$-chloroformylcyclopentadienyl)-manganese tricarbonyl. However, ($\eta\sp5$-cyclopentadienyl)carbonyl(triphenylphosphine)cobalt is unreactive to Friedel-Crafts' acylation. Infrared and NMR studies of the acylation of ($\eta\sp5$-cyclopentadienyl)carbonyl(triphenyl-phosphine)cobalt indicate that this compound contains many reactive sites, with the cyclopentadienyl ring being the less favored. Analogous spectral studies of ($\eta\sp5$-cyclopentadienyl)dicarbonylcobalt support acylation of the cyclopentadienyl ring but also suggest other sites for reaction. All ketones derived from ($\eta\sp5$-cyclopentadienyl)dicarbonylcobalt have been reacted with triphenylphosphine and/or diphenylacetylene to give the phosphine and/or tetraphenylcyclobutadiene derivatives. Ketone derivatives of ($\eta\sp5$-cyclopentadienyl)($\eta \sp4$-tetraphenylcyclobutadiene)cobalt have been shown to undergo typical organic reactions: lithium aluminum hydride/aluminum chloride reduction, sodium borohydride reduction, and the Wittig reaction. ($\eta\sp5$-Carbomethoxycyclopentadienyl)($\eta \sp4$-tetraphenylcyclobutadiene)cobalt has been synthesized and used for the preparation of the following derivatives: ($\eta\sp5$-carboxycyclopentadienyl)($\eta \sp4$-tetraphenylcyclobutadiene)-cobalt, ($\eta\sp5$-chloroformylcyclopentadienyl)($\eta \sp4$-tetraphenylcyclobutadiene)-cobalt, ($\eta\sp5$-carbamoylcyclopentadienyl)($\eta \sp4$-tetraphenylcyclobutadiene)cobalt, ($\eta\sp5$-cyanocyclopentadienyl)($\eta \sp4$-tetraphenylcyclobutadiene)cobalt, and bis- (($\eta\sp5$-carboxycyclopentadienyl)($\eta \sp4$-tetraphenylcyclobutadiene)cobalt) anhydride. The preparation of a pinacol from ($\eta\sp5$-benzoylcyclopentadienyl)-($\eta \sp4$-tetraphenylcyclobutadiene)cobalt has been attempted. Two products have been isolated. ($\eta\sp5$-Chloroformylcyclopentadienyl)($\eta \sp4$-tetraphenylcyclobutadiene)cobalt has been demonstrated to react with ferrocene to give the corresponding heterobimetallic compound. Other heterobimetallics have been prepared from ($\eta\sp5$-cyclopentadienyl)dicarbonylcobalt and ($\eta\sp5$-chloroformylcyclopentadienyl)($\eta \sp5$-cyclopentadienyl)iron, bis($\eta\sp5$-chloroformylcyclopentadienyl)iron, or ($\eta\sp5$-chloroformylcyclopentadienyl)manganese tricarbonyl.
| Identifer | oai:union.ndltd.org:UMASS/oai:scholarworks.umass.edu:dissertations-9016 |
| Date | 01 January 1994 |
| Creators | Mabrouk, Suzanne Theresa |
| Publisher | ScholarWorks@UMass Amherst |
| Source Sets | University of Massachusetts, Amherst |
| Language | English |
| Detected Language | English |
| Type | text |
| Source | Doctoral Dissertations Available from Proquest |
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