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Issue 23, 2016
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A 1,2,3-dithiazolyl-o-naphthoquinone: a neutral radical with isolable cation and anion oxidation states

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Abstract

Under aprotic conditions, the reaction of 4-amino-1,2-naphthoquinone with excess S2Cl2 generates 4,5-dioxo-naphtho[1,2-d][1,2,3]dithiazol-2-ium chloride in a typical Herz condensation. By contrast, prior literature reports an imine (NH) product, 4,5-dioxo-1H-naphtho[1,2-d][1,2,3]dithiazole, for the same reaction performed in acetic acid. Herein, the cation product is isolated with four different counter-anions (Cl, GaCl4, FeCl4 and OTf). Reduction of the cation generates a neutral radical 1,2,3-dithiazolyl-o-naphthoquinone, with potential ligand properties. Further reduction generates a closed shell anion, isolated as a water-stable Li+ complex and exhibiting O,O-bidentate chelation. The hydroxy (OH) isomer of the original imine (NH) product is reported, and this can be readily deprotonated and acylated (OAc). All species are structurally characterized. Solution redox behaviour and EPR are discussed where appropriate.

Graphical abstract: A 1,2,3-dithiazolyl-o-naphthoquinone: a neutral radical with isolable cation and anion oxidation states

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Article information


Submitted
31 Mar 2016
Accepted
18 May 2016
First published
24 May 2016

Dalton Trans., 2016,45, 9608-9620
Article type
Paper
Author version available

A 1,2,3-dithiazolyl-o-naphthoquinone: a neutral radical with isolable cation and anion oxidation states

C. S. Smithson, D. J. MacDonald, T. Matt Letvenuk, C. E. Carello, M. Jennings, A. J. Lough, J. Britten, A. Decken and K. E. Preuss, Dalton Trans., 2016, 45, 9608
DOI: 10.1039/C6DT01249C

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