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Gaganatsou, Paraskevi (1987) Lithium and indium quinoneoximic complexes and their application in scintillation counting. Doctoral thesis, Polytechnic of North London.
Several complexes of lithium derived from 1,2-naphthoquinone 1-oxime and 1,2-naphthoquinone 2-oxime have been prepared and characterised using analytical, spectroscopic and thermal gravimetric techniques. I.r. studies indicate that the ligands in these complexes are essentially quinoneoximic in character. For the complex Li(1-nqo)(1-nqoH).Eton the quinoneoximic character has been confirmed by X-ray crystallography.
All the lithium complexes were found to be stable towards atmospheric oxygen and water. Their reactivity towards dimethylacetylene dicarboxylate was investigated and compared to that of the copper quinoneoximato complexes. Each of the lithium complexes reacted readily with the acetylene dicarboxylate to give a novel nucleophilic addition product isomeric to the Diels-Alder adduct (1,4-oxazine) obtained from the copper complexes. Re-examination of the behaviour of the copper quinoneoximato complexes towards dimethylacetylene dicarboxylate has given an insight to the mechanism of the reaction and has shown that the copper complexes also act as catalysts in the conversion of 1,4-oxazine derivatives to 1,3-oxazoles.
Several lithium carboxylato and dithiocarbamato complexes have been prepared. For the dithiocarbamato complexes a new synthetic method involving the reaction of carbon disulphide and the amine with lithium chloride was developed during this study.
Solubility studies were carried out on several complexes of types Li(RCO,), Li(R-NCS,)(R-NCSSH), Ll(nqo) and M(qo) (M = Li, Na2 K, Ni, Co) in polar and non-polar solvents. Maximum solubility was observed in pyridine, dimethylsulphoxlde and ethanol.
The scintillation efficiency of pyridine, dimethylsulphoxide and ethanol was examined in commercially available scintillator mixtures and in scintillator mixtures developed during this study. The scintillation efficiency of the lithium complexes derived from the mono-oximes of 1,2-naphthoqulnone, carboxylic and dlthlocarbamlc acids was also investigated. The latter two set of complexes proved promising for loading liquid scintillation counters, when present as 'solid' in the scintillator mixture.
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