Steric influence on hapto interactions in supramolecularly linked thallium dithiocarbamates

Spectral and structural characterization of diallyl and dibenzyl dithiocarbamates of thallium(I) indicated increased thalliocarbon hapto interactions in dibenzyl dithiocarbamate due to increased steric effects. Proton magnetic resonance spectra of the compounds showed that the protons in the vicinity of the thioureide nitrogen are highly deshielded and the corresponding 13C spectra showed large chemical shifts of the thioureide carbons due to decreased electron density. Cyclic voltammetry and bond valence calculations established that the oxidation number of thallium was +1. The Tl–S bond distances in both compounds did not vary significantly. η1–Tl···C(S2) supramolecular interactions were observed in both compounds. A nonclassical S···H bond (2.841 Å) was also observed in the dibenzyl compound. Aside from the two noncovalent interactions mentioned, additional hapto interactions such as Tl(1)S2η1Cη1Cη2C2 and Tl(2)S2η1Cη3C3 were observed. Both compounds formed polymeric chains through hapto interactions.