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Issue 24, 2005
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EPR studies on the thiophenodithiazolyl radical, C4H2S3

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Abstract

Selective chlorination of thiophene-2,3-dithiol with SO2Cl2 generates the corresponding sulfenyl chloride, 2,3-C4H2S(SCl)2. Subsequent condensation with Me3SiN3 yields the thiophenodithiazolylium salt [C4H2S3N]Cl, [TDTA]Cl. The structure of the cation, TDTA+, was established by X-ray diffraction as both its AsF6 and HSO4 salts. Reduction of [TDTA]Cl with Ag powder yields the radical TDTA˙ which was characterised by X- and Q-band (9 and 34 GHz) EPR and ENDOR studies. The spin density distributions estimated from the EPR/ENDOR measurements were found to be in very good agreement with those determined by DFT (B3LYP/6-31G*) indicating that ca 10% of the spin density is delocalised onto the thiophene ring. Comparison of the spin density distributions in TDTA˙ and the isoelectronic trithiatriazapentalenyl radical C2S3N3, TTTA˙, indicates that replacement of N by C–H leads to a localisation of the spin density on the dithiazolyl ring.

Graphical abstract: EPR studies on the thiophenodithiazolyl radical, C4H2S3N˙

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Article information


Submitted
24 Jun 2005
Accepted
06 Sep 2005
First published
05 Oct 2005

Dalton Trans., 2005, 3838-3845
Article type
Paper

EPR studies on the thiophenodithiazolyl radical, C4H2S3

A. Alberola, R. D. Farley, S. M. Humphrey, G. D. McManus, D. M. Murphy and J. M. Rawson, Dalton Trans., 2005, 3838
DOI: 10.1039/B508912C

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