Some iron and manganese complexes of heterocycles

Qazi, Abdurrasool R (1965) Some iron and manganese complexes of heterocycles. PhD thesis, University of Glasgow.

Abstract

The study describes the various attempts which have been made to synthesize heterocyclic derivatives of transition metals, e.g. iron and manganese, in which the heterocycle is bonded to the metal in an analogous manner to the bonding in pi-cyclopentadienyl-metal compounds. The pi pyrrolyl manganese carbonyl complexes were prepared by one or both or the following methods. In the first the pyrrole or substituted pyrrole was heated with dimanganese decacarbonyl in an inert solvents. In the second method, the potassium salt of the heterocycle was heated with bromomanganese pentacarbonyl. The latter method was found to be more widely applicable and was extended to the preparation of such complexes from pyrroles bearing functional groups, to indoles, pyrazoles and benzotriazole. In some of these cases a-heterocycle manganese pentacarbonyl could be isolated as the first products Similarly the potassium salt of heterocycles containing nitrogen, on reaction with iodo-dicarbonyl cyclopentadienyl iron gave a-complexes, i.e. dicarbonyl-pi-cyclopentadienyl-a-heterocycle iron. These a-bonded complexes by loss of carbon monoxide yielded aza ferrocenes, i.e. pi-cyclopentadienyl-pi-heterocycle iron at higher temperature. Attempts to effect electrophilic substitution of the two parent complexes, i.e. trioarbonyl-pi-pyrrolyl manganese and pi-cyclopentadienyl-pi-pyrrolyl iron were made in order to prepare beterocyclio metal complexes with functional groups. Friedel and Crafts Acylation appeared to give a trace of acylated products, while apiempted aminomethylation resulted in decomposition. The reaction of pyrroyl chloride with sodlomanganese pentacarbonyl resulted in the formation of the a-bonded complex, 2-pyrrolyl manganese pentacarbonyl via pyrroyl manganese pentacarbonyl by loss of carbon monoxide. Allyl iron tricarbonyl iodide on reaction with pyrrolyl potassium gave 2 : 4 Hexadiene tricarbonyl iron. Unsuccessful apiempts have been made to prepare dipyxrolyl analogous of ferrocene, cobaltocene and niokelocene. The reaction between molyledenum hexacarbonyl and pyrrolyl potassium resulted in decomposition.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Additional Information: Adviser: P L Pauson
• Keywords: Inorganic chemistry, Organic chemistry
• Date of Award: 1965
• Depositing User: Enlighten Team
• Unique ID: glathesis:1965-73804
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 14 Jun 2019 08:56
• Last Modified: 14 Jun 2019 08:56
• URI: https://theses.gla.ac.uk/id/eprint/73804