Organometallic compounds of the 1,3-dithiole-2-thione-4,5-dithiolate (DMIT) ligand
Compounds of the form R2Sn(dmit) (H2dmit = dimercaptoisotrithione) (R = Me, Et, Bu, Oct, Ph, o-MeOC6H4. MeO2CCH2CH2 and PriO2CCH2CH2) and RR'Sn(dmit) (R = Ph, R' = Me) were synthesised and characterised. Five of the compounds were further investigated using solid state 13C and 119Sn nmr and Mossbauer spectroscopy. The crystal structure of the compounds Et2Sn(dmit), (MeO2CCH2CH2)2Sn(dmit) and PhMeSn(dmit) were determined, and attempts were made to correlate these structures with the solid state nmr data. The addition of a halide ion to the tin atom in the compounds R2Sn(dmit) to give the anion [R2Sn(dmit)X]- (X = halogen) by reaction with a suitable onium halide was investigated. Substitution of the halide, X, in these [Y][R2Sn(dmit)X] (Y = onium cation) compounds was investigated using alkali metal halides and pseudohalides. The crystal structures of the compounds [1,4-dimethylpyridinium][Ph2Sn(dmit)NCS] and [1,4-dimethylpyridinium][Ph2Sn(dmit)I] were determined. The monoestertin bis-dmit complex [NEt4][MeO2CCH2CH2Sn(dmit)2], and the tin tris-dmit complexes. [NR4]2[Sn(dmit)3] (NR4 = NEt4 and 1,4- dimethylpyridinium), were prepared.. The crystal structures of [NEt4][MeO2CCH2CH2Sn(dmit)2] and [NEt4]2[Sn(dmit)3] were determined. A range of lead-dmit complexes, namely PbII(dmit), Ph2Pb(dmit), (Ph3Pb)2dmit and [NR4][Ph2(dmit)I] (NR4 = NEt4 and 1,4-dimethylpyridinium) was also synthesised. The crystal structure of (Ph3Pb)2dmit was determined, and cyclic voltammetry studies were carried out on Ph2Pb(dmit) and (Ph3Pb)2dmit.