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Selective oxidation of adamantane by metal complexes

A series of tri-substituted iron and cobalt complexes of the form [M(A)3]n+ were synthesized, and were characterised by UV/Visible absorption and 1H-NMR spectroscopy. The complexes [Co(phen)2(en)]3+ and [Co(bipy)2(en)]3+ have been reported in the literature but 1H-NMR spectroscopy showed that the material produced in both syntheses is [Co(en)3]3+. Spectroscopy further showed that these species cannot be prepared by the literature methods. The complexes were tested in the oxidation of adamantane in the solvents, acetic acid and trifluoroacetic acid and they all oxidised adamantane to a mixture of 1-adamantanol, 1-adamantanol and 2-adamantanone both in the presence and the absence of the oxidant, O2. In all the reactions, however, the yield of conversion was very low. The mechanism for this oxidation was different depending on the presence or absence of O2. In the presence of O2 a catalytic cycle was produced for the oxidation of adamantine. In the oxidation in the presence and absence of O2 there was little variation in activity between the tri-substituted iron and cobalt complexes of 1,10-phenanthroline when compared with the analgous 2,2’-bipyridine complexes. However, the substitution of an ethylenediamine ligand into the co-ordination sphere of cobalt produced significant increase in the activity, although the change was not constant. / Master of Science (Hons)

Identiferoai:union.ndltd.org:ADTP/235310
Date January 1997
CreatorsRaviJayaKumar, K., University of Western Sydney, Faculty of Science and Technology
Source SetsAustraliasian Digital Theses Program
LanguageEnglish
Detected LanguageEnglish
SourceTHESIS_FST_XXX_RaviJayaKumar_ K.xml

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