title: 1,5,2,4,6,8-Dithiatetrazocine. Synthesis, computation, crystallography and voltammetry of the parent heterocycle.
abstract: The prototypal 1,5,2,4,6,8-dithiatetrazocine has been synthesized for the first time by two routes: reaction of 1,2,3,5-dithiadiazolium chloride with N,N,N'-tris(trimethylsilyl)formamidine in acetonitrile and reaction of 1,2,3,5-dithiadiazolyl radical with dioxygen in solution. Yields are low but single crystals could be obtained for an X-ray crystal structure determination which shows it to have the planar delocalized structure predicted by B3LYP/6-311+G(2d,p) hybrid DFT calculations. The crystal structure is strongly reminiscent of that of benzene in the same Pbca space group. Aromaticity is demonstrated by a (1)H NMR chemical shift of +9.70 ppm indicative of diamagnetic ring shielding and an intense low-energy optical absorption with λ(max) = 349 nm (MeOH). The voltammetric behaviour of the title compound is compared with that of 1,3λ(4)δ(2),5,2,4-trithiadiazepine; both resist electrochemical oxidation and reduction over a wide potential range as is typical for aromatic heterocycles.
authors.affiliation: Moock Environmental Solutions Ltd., 6a Mid Road, Blairlinn Industrial Estate, Cumbernauld, G67 2TT, UK. moock-ltd@tiscali.co.uk
authors.forename: Klaus H
authors.initials: KH
authors.lastname: Moock
authors.forename: Ken M
authors.initials: KM
authors.lastname: Wong
authors.forename: René T
authors.initials: RT
authors.lastname: Boeré