Syntheses and structures of diorgano(halo- or pseudohalo-) (1,3-dithiole-2-thione-4,5-dithiolato)-stannates (1-), [Q] [R2SnX(dmit)] (Q = onium cation; X = halide or pseudohalide)
Jh. Aupers et al., Syntheses and structures of diorgano(halo- or pseudohalo-) (1,3-dithiole-2-thione-4,5-dithiolato)-stannates (1-), [Q] [R2SnX(dmit)] (Q = onium cation; X = halide or pseudohalide), POLYHEDRON, 17(25-26), 1998, pp. 4475-4486
Ionic compounds, [Q] [R2SnX(dmit)] [dmit = 1,3-dithiole-2-thione-dithiolate
; Q = 1,4-dimethlpyridinium or tetraalkylammonium R = Ph or alkyl; X = Cl,
Br, I, NCS, NCSe, or N-3] have been obtained by (a) from R2SnX2 and [Q](2)[
Zn(dmit)(2)] in the presence of excess QX, (b) from halide exchange reactio
ns in acetone solution between [Q] [R2SnCl(dmit)] and a halide or pseudohal
ide source, or (c) by addition of QX to [R2Sn(dmit)]. Crystal structure det
erminations of [NEt4] [Ph2SnI(dmit)] and [1,4-Me(2)pyridinium] [Ph2SnBr(dmi
t)] as well as of the mixed halides. [1,4-Me(2)pyridinium] [Ph2SnCln,I(1-)n
(dmit)] (n = 0.57, 0.42 or 0.22), indicated that the till atoms have distor
ted trigonal bipyramidal geometries in the anions: with the X ligand and a
dithiolato atom in the axial sites. The [R2SnX(dmit)](-) anions remain esse
ntially intact in organic solvents, but lose X- on extraction with H2O to g
ive the neutral species, R2Sn(dmit). (C) 1998 Elsevier Science Ltd. All rig
hts reserved.