Preparation and properties of tin(IV) complexes with the sulfur-rich dithiolate C3S5 and C8H4S8 ligands and their oxidation

[NMe4](2)[Sn(C3S5)(3)], [NBu4n](2)[Sn(C3S5)(3)], [NBu4n](2)[Sn(C8H4S8)(3)], [NEt4][Sn(Bu-n)(C8H4S8)(2)] and [NBu4n][Sn(Ph)(C8H4S8)(2)] [C3S52- = 4,5-disulfanyl-1,3-dithiole-2-thionate(2-); C8H4S82- = 2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-ditholate(2-)] were prepared by reactions of Na-2[C3S5] or Na-2[C8H4S8] with SnCl4.5H(2)O, Sn(Bu-n)Cl-3 and Sn(Ph)Cl-3 in EtOH. [NBu4n](2)[Sn(C8H4S8)(3)] was oxidized by iodine or TCNQ in DMF/CH2Cl2 to give [Sn(C8H4S8)(3)], which exhibited an electrical conductivity of 3.2 X 10(-2) S cm(-1) (compacted pellet at room temperature). [NBu4n](2)[Sn(C3S5)(3)], [NEt4][Sn(Bu-n)(C8H4S8)(2)] and [NBu4n][Sn(Ph)(C8H4S8)(2)] were oxidized by iodine or TCNQ in acetone or in DMF to afford (C3S5)(2) and (C8H4S8)(2). Crystal structures of [NMe4](2)[Sn(C3S5)(2)], [NBu4n](2)[Sn(C3S5)(3)], [NBu4n][Sn(Ph)(C8H4S8)(2)] and (C3S5)(2) were determined by X-ray crystallography.