Issue 43, 2011

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 1H NMR chemical shift of +9.70 ppm indicative of diamagnetic ring shielding and an intense low-energy optical absorption with λmax = 349 nm (MeOH). The voltammetric behaviour of the title compound is compared with that of 1,3λ4δ2,5,2,4-trithiadiazepine; both resist electrochemical oxidation and reduction over a wide potential range as is typical for aromatic heterocycles.

Graphical abstract: 1,5,2,4,6,8-Dithiatetrazocine. Synthesis, computation, crystallography and voltammetry of the parent heterocycle

Supplementary files

Article information

Article type
Paper
Submitted
27 Jul 2011
Accepted
22 Aug 2011
First published
28 Sep 2011

Dalton Trans., 2011,40, 11599-11604

1,5,2,4,6,8-Dithiatetrazocine. Synthesis, computation, crystallography and voltammetry of the parent heterocycle

K. H. Moock, K. M. Wong and R. T. Boeré, Dalton Trans., 2011, 40, 11599 DOI: 10.1039/C1DT11418B

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