SYNTHESES AND PROPERTIES OF THE LEAD 1,3-DITHIOLE-2-THIONE-4,5-DITHIOLATE (DMIT) COMPOUNDS - PH(2)PB(DMIT), [Q] [PH(2)PB(DMIT)-I] [Q=NET(4)OR 1,4-ME(2)-PYRIDINIUM], (PH(3)PB)(2)(DMIT) AND PB(DMIT)

Syntheses of Ph(2)Pb(dmit) (3), [Q] [Ph(2)Pb(dmit)I] (5, Q = NEt(4) or 1,4-Me(2)-pyridinium), (Ph(3)Pb)(2)(dmit) (4) and Pb(dmit) (6) are re ported [H-2-dmit = 4,5-dimercapto-1,3-dithiole-2-thione]. Compound 3 w as produced from Ph(2)Pb(OAc)(2) and [NEt(4)](2)[Zn (dmit)(2)], while 4 was obtained from Ph(3)PbOAc and either Na-2(dmit) or [NEt(4)](2)[Zn (dmit)2]. The ionic species, 5, were obtained by addition of [Q] I to 3 (eg. for Q = 1,4-Me(2)-pyridinium) or from reaction of Ph(2)PbI(2) w ith [NEt(4)](2)[Zn(dmit)(2)]. Reaction of either Pb(OAc)(2) or Pb(NO3) (2) with [NEt(4)](2)[Zn(dmit)(2)] produced 6. NMR spectra, including t he solid state spectra for 3, have been obtained. X-ray crystallograph y revealed 4 to be a monomeric compound with each Pb atom having a dis torted tetrahedral geometry. The C-Pb-S bond angles are less and the C -Pb-C bond angles greater than ideal tetrahedral angles. The dmit liga nd is effectively inserted between two phenyl rings of different Ph(3) Pb groups in 4, with short non-bonded C-C and C-S distances of 3.4-3.7 Angstrom. Cyclic voltammetric studies of 3 and of 4 in DMF have also been carried out.