Picture of DNA strand

Pioneering chemical biology & medicinal chemistry through Open Access research...

Strathprints makes available scholarly Open Access content by researchers in the Department of Pure & Applied Chemistry, based within the Faculty of Science.

Research here spans a wide range of topics from analytical chemistry to materials science, and from biological chemistry to theoretical chemistry. The specific work in chemical biology and medicinal chemistry, as an example, encompasses pioneering techniques in synthesis, bioinformatics, nucleic acid chemistry, amino acid chemistry, heterocyclic chemistry, biophysical chemistry and NMR spectroscopy.

Explore the Open Access research of the Department of Pure & Applied Chemistry. Or explore all of Strathclyde's Open Access research...

Reaction of thiones with dihalogens: comparison of the solid state structures of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione-diiodine, -dibromine and -iodine monobromide

Bricklebank, N. and Skabara, P.J. and Hibbs, D.E. and Hursthouse, M.B. and Malik, K.M.A. (1999) Reaction of thiones with dihalogens: comparison of the solid state structures of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione-diiodine, -dibromine and -iodine monobromide. Journal of the Chemical Society, Dalton Transactions, 1999 (17). pp. 3007-3014. ISSN 0300-9246

Full text not available in this repository.Request a copy from the Strathclyde author

Abstract

Reaction of 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione 1 with diiodine or iodine monobromide in CH2Cl2 resulted in the formation of molecular charge-transfer complexes 1 . I-2 and 1 . IBr respectively. Both complexes have been characterised crystallographically and contain a linear S-I-X (X = I or Br) moiety with the sulfur adopting a tetrahedral geometry taking into account the stereochemically active lone pairs. The S-I [2.716(3)] and I-I [2.808(3) Angstrom] bond lengths in 1 . I-2 are similar to those reported for diiodine complexes of related thione donors. The adduct 1 . IBr is the first crystallographically characterised thione-iodine monobromide charge-transfer complex. The S-I distance [2.589(2) Angstrom] is shorter than that in 1 . I-2, consistent with IBr being a stronger acceptor than I-2. The I-Br distance [2.7138(11) Angstrom] is lengthened with respect to that in unco-ordinated IBr, but within bonding distance when compared to the sum of the van der Waals radii for iodine and bromine (3.75 Angstrom). Treatment of 1 with dibromine under identical conditions resulted in the formation of the adduct 1 . Br-2 and the dithiolylium salt [C5H6S4Br][Br-3]. 1/2Br(2) 2. Treatment of 1 with Br-2 in toluene led to the isolation of 1 . Br-2 only. The crystal structure of 1 . Br-2 shows the compound to contain a linear Br-S-Br moiety with the sulfur in a T-shaped or Psi-trigonal bipyramidal environment (taking into account the stereochemically active lone pairs). The structure of 2 reveals a three component system consisting of the [C5H6S4Br](+) cation, the [Br-3](-) anion and a molecule of Br-2 in a 2:2:1 ratio. These components are held in the lattice by a series of weak intermolecular interactions which link the tribromide ions and dibromine molecules into zigzag chains.