SYNTHESIS AND CHARACTERIZATION OF TETRAETHYLAMMONIUM AND 1,4-DIMETHYLPYRIDINIUM ANTIMONY(III) BIS-DMIT COMPLEXES

SMSV DOIDGEHARRISON*, John Thomas Sirr Irvine, GM SPENCER, JL WARDELL, M WEI, P GANIS, G VALLE

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

36 Citations (Scopus)

Abstract

The synthesis and characterisation of two novel antimony (III) bis-dmit complexes are reported [H-2-dmit = 4,5-dimercapto-1, 3-dithiole-2-thione]. Compounds [Y][Sb(dmit)(2)] [Y = Et(4)N (1) and Y = C7H10N (1,4-dimethylpyridinium) (2)] are the first main group dmit complexes to show significant metal-sulfur interanionic interaction in the solid state. The [Sb(dmit)(2)](-) anions in both complexes contain strong Sb-S primary bonds arranged to give pseudo trigonal bipyramidal antimony atoms (lone pair of electrons in equatorial site; axial (Sb-S) mean 2.67 Angstrom and equatorial (Sb-S) mean = 2.50 Angstrom). Secondary Sb- - -S interanionic interactions have been revealed by X-ray crystallography. Details of the crystal structures are as follows 1, monoclinic, C2/c, a = 12.391(7) Angstrom, b = 13.090(7) Angstrom, c 15.587(8) Angstrom, beta = 102.7(1)degrees, V = 2466.3 Angstrom(3), Z = 4; for 2, triclinic, P (1) over bar, a = 8.986(5) Angstrom, b = 10.983(6) Angstrom, c = 11.365(6) Angstrom, alpha = 87.1(1)degrees, beta = 74.3(2)degrees, gamma = 88.0(1)degrees, V = 1245.2 Angstrom(3), Z = 2. The crystal structure of 1 consists of a polymeric two dimensional network formed by the bridging of Sb atoms and terminal S atoms of adjacent molecules. In contrast, the crystal structure of 2 consists of anionic dimers, although this structure also involves bridging between Sb atoms and terminal S atoms. In both cases the Sb- - -S interanionic distances are about 3.3 Angstrom, which is 0.6 Angstrom shorter than the sum of the van der Waals radii of Sb and S. Cyclic voltammetry studies of 1 in dimethylformamide show an oxidation wave and an associated reduction wave. The large separation, 0.7 V, between these is indicative of an intervening chemical reaction.

Original languageEnglish
Pages (from-to)4581-4584
Number of pages4
JournalInorganic Chemistry
Volume34
Issue number18
Publication statusPublished - 30 Aug 1995

Keywords

  • MOLECULAR SUPERCONDUCTOR
  • CRYSTAL
  • <(CH3)4N><NI(DMIT)2>2
  • PRESSURE
  • 1,3-DITHIOLE-2-THIONE-4,5-DITHIOLATE DMIT

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