Formation of indium(III) 1,3-dithiole-2-thione-4,5-dithiolate anions, [In(dmit)(2)](1-) and [In(dmit)](3-). Crystal structure of Cs[In(dmit)(2)]: Strong cation-anion interactions

摘要

The preparations of [In-III(dmit)(n)](m) (m,n = 1,2 or 3,3) salts, using [Na](2)[dmit] and [Cs](2)[dmit] as dmit sources, are reported ([dmit](2) = 1,3-dithiole-2-thione-4,5-dithiolate). Characterizations were generally achieved via elemental analyses and IR spectroscopy. Compounds, [Q][In-III (dmit)(2)] (Q = NMe4, PPh4 and AsPh4) were generally obtained using mole ratios of [Na](2)[dmit]:QX (X = halide): InCl3 of 2:1:1. However, using [Cs](2)[dmit] with the same addition sequence of reagents and a similar mole ratio of reagents, mixed cation salts, [Q](y)[Cs](1-y)[In(dmit)(2)] (e.g., Q, y = NBu4, 0.323; PPh4, 0.437), were isolated. Tris(dmit) salts, [In-III(dmit)(3)](3), were invariably obtained using reagent mole ratios of [Cs](2)[dmit]:[Q]X:InCl3 = 3:3:1 in MeOH solution. However only with the bulkiest cations, (Q(+) = [AsPh4](+) or [PPh4](+)), were single salts, [Q](3)[In(dmit)(3)], obtained. For less bulky cations, such as (Q(+) = [NBu4]+ or [NMe4](+)), compounds isolated had mixed cations, [Q]x[Cs](3) x[In-III(dmit)(3)].