EPR studies on the thiophenodithiazolyl radical, C4H2S3N˙

Alberola, Antonio, Farley, Robert D., Humphrey, Simon M., McManus, Gordon D., Murphy, Damien Martin ORCID: https://orcid.org/0000-0002-5941-4879 and Rawson, Jeremy M. 2005. EPR studies on the thiophenodithiazolyl radical, C4H2S3N˙. Dalton Transactions (24) , pp. 3838-3845. 10.1039/b508912c

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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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	RSC
ISSN:	1477-9226
Last Modified:	18 Oct 2022 13:12
URI:	https://orca.cardiff.ac.uk/id/eprint/12996

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