Photochemistry of Some Metal Carbonyls in Frozen Solvent Glasses

Black, John D (1974) Photochemistry of Some Metal Carbonyls in Frozen Solvent Glasses. PhD thesis, University of Glasgow.

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Photolysis reactions of Fe(CO)5, group VI hexacarbonyls, some substituted group VI hexacarbonyl derivatives, and cyclopentadienyl manganese tricarbonyl and some related compounds in hydrocarbon glass have been examined. Reactions in the more reactive glass. 2-methyltetrahydrofuran, and reactions of the above species in hydrocarbon glass in the presence of some potential ligands have also been examined. The glass temperature throughout this work was 77K. Reaction monitoring throughout was by i. r. spectroscopy, mostly observing the carbonyl stretching region only, and the object of the work was to observe the results of photolysis in glasses and to correlate these with results obtained in very low temperature gas matrices and in solution by other workers rather than to determine the actual photolysis mechanisms. In many experiments glasses containing photolysis fragments were deliberately allowed to warm up beyond the glass softening temperature and the changes occurring on glass softening were monitored in an attempt to link the results obtained in the glasses with results of photolysis in solution where molecules are free to associate. The predominant reaction in all the systems studied in glasses was stepwise CO loss, and many CO deficient fragments have been observed and identified as far as is possible from their i. r. spectra. In cases where the results of matrix isolation studies were available the results obtained in this work are consistent with these. The results obtained in hydrocarbon glass also support the view that saturated hydrocarbon interacts with CO deficient metal carbonyl fragments to an extent not realised until very recently. Another point of general interest which has arisen from the photolysis reactions in hydrocarbon in the presence of added donors is the importance of pre-photolytic association of carbonyl and potential ligand. The possible effect of this type of association on solution photochemical reactions does not seem to have been previously recognised and should certainly be investigated.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Organic chemistry, Physical chemistry
Date of Award: 1974
Depositing User: Enlighten Team
Unique ID: glathesis:1974-78684
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 30 Jan 2020 15:02
Last Modified: 30 Jan 2020 15:02

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