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 reported [H-2-dmit = 4,5-dimercapto-1,3-dithiole-2-thione]. Compound 3 was 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) with [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 the solid state spectra for 3, have been obtained. X-ray crystallography revealed 4 to be a monomeric compound with each Pb atom having a distorted tetrahedral geometry. The C-Pb-S bond angles are less and the C-Pb-C bond angles greater than ideal tetrahedral angles. The dmit ligand 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.