Some Substitution Reactions of Metal Carbonyls

Stubbs, William Hamilton (1963) Some Substitution Reactions of Metal Carbonyls. PhD thesis, University of Glasgow.

Abstract

The first part of this study describes the substitution reactions of various metal carbonyl derivatives with phonyl-isocyanidoc Qualitative studies of the substitution of halo-manganese carbonyls have shown the ease of substitution to increase in the order iodide, bromide chloride. Complete stepwise replacement of the carbonyl groups in bromo-penta-carbonylmanganese has been achieved by variation of the reaction solvent and temperature. Similar substitution reactions with the cyclopentadienyl metal carbonyl halides of iron and molybdenum have also shown the degree of substitution to vary with the electronegativity of the halogen used. Reduction of the mono substituted iron complex; iodo-carbonylphenylisocyanidecyclopentadienyliron has been found to give a dimeric complex containing a 'bridging' isocyanido group similar to the well established 'bridging' carbonyl groups of metal complexes. Substitution reactions of methyl and phenylmanganese-pentacarbonyl with phenylisocyanide have been found to give a mixture of mono and di-substituted, derivatives of dimanganese decacarbonyl. This is in contrast to the reactions of the pentacarbonyls with carbon monoxide and amines, which are reported to give the acetyl and benzoyl derivatives. The isocyanide analogues of tricarbonylcyclopenta-dlenylmanganese and di(carbonyIcyclopentadienylnickel) have boon synthesised. The second part of this study describes the various attempts which have been made to prepare heterocyclic derivatives of metal carbonyl, in which the heterocycle is bonded to the metal in an analogous manner to the bonding in metal-pi-cyclopentadienyl compounds. Reaction of 2-methylpyrrole and manganese carbonyl has been found to give tricarbonyl-2-methylpyrrolylmanganese. Pyrrolyl potassium has been found to react with iodo-dicarbonylcyelopentadlenyl-iron to give pyrrolylcyclopentadienyliron. Unsuccessful attempts were made to prepare the pyrrole analogues of ferrocene and nickelocene.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1963
• Depositing User: Enlighten Team
• Unique ID: glathesis:1963-79482
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 05 Mar 2020 09:05
• Last Modified: 05 Mar 2020 09:05
• URI: https://theses.gla.ac.uk/id/eprint/79482