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Tice, P. A. (1960) Infrared and chemical studies of some metal xanthates and related compounds. Doctoral thesis, Sir John Cass College.
A number of metal methyl and ethyl xanthates have been investigated with the primary view of determining their basic structures. The infrared spectra of these metal xanthates were obtained, and, as a first step in the structural determination, an attempt was made to assign the vibrational modes of the molecules. As the vibrational assignment of the metal xanthates was complex, similar but simpler compounds were investigated. These compounds included thiophosgene, some trithiocarbonate acids and esters and also some xanthate acids and esters. Reasonably complete vibrational assignments were made for these compounds, which were then found useful in assigning the vibrational modes of the metal xanthates.
In the investigation of the trithiocarbonate and xanthate acids, it was found that they exhibit weak hydrogen bonding and also rotational isomerism.
The metal methyl and ethyl xanthates have been divided into two groups on the basis of the frequency values of the vc=s vibration, one with values of the order of 1200 cm-1, the other with values of 1250 cm-1 or above. It has been postulated that the latter metal xanthates probably have structures involving four membered rings. For the former metal xanthates it is thought that these four membered ring structures do not predominate.
The thermal stabilities of a number of metal methyl xanthates were also investigated, but no definite structural information was obtained, although a division was made, depending on whether the decompositions were exothermic or endothermic, which agreed in general with the two groups previously postulated on the infrared evidence.
The infrared spectra of some metal alkyl trithiocarbonates were examined, and from the results it was found possible to postulate a number of probable structures, although not to establish any definitely.
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