MAIN GROUP METAL 1,3-DITHIOLE-2-THIONE-4,5-DITHIOLATO (DMIT) COMPOUNDS .3. SYNTHESIS OF TETRABUTYLAMMONIUM BIS(1,3-DITHIOLE-2-THIONE-4,5-DITHIOLATO)DIHALOSTANNATES - CRYSTAL-STRUCTURE OF [BU4N]2[I2SN(DMIT)2]

Compounds [Bu4N]2[X2Sn(DMIT)2] [X = Br (4) or 1 (5); H2-DMIT = 4,5-dimercapto-1,3-dithiole-2-thione] have been prepared from [Bu4N]2[Zn(DMIT)2] and SnX4 in the presence of Bu4NBr. A crystal structure determination of 5 revealed it to consist of discrete [Bu4N] cations and [I2Sn(DMIT)2] dianions; the geometry about tin in the dianion is octahedral with chelating DMIT ligands and cis-iodide ligands [Sn-I = 2.724(5) and 2.727(3) angstrom; mean Sn-S (trans to I) = 2.560 angstrom and mean Sn-S (trans to S) = 2.530 angstrom]. The chelate bite angles are 82.9(4) and 83.1(4)-degrees.</p

Diorganotin 1,3-dithiole-2-thione-4,5-dithiolate compounds, R(2)Sn(dmit): The crystal structure of MePhSn(dmit)

Neutral diorganotin dmit compounds, R(2)Sn(dmit), have been synthesised from R(2)SnX(2) (R = Me, Et, Bu, octyl, Ph or o-MeOC(6)H(4); R(2) = Ph,Me; X = Cl or Br) and [NEt(4)](2)[Zn(dmit)(2)] (H-2-dmit = 4,5-dimercapto-1,3-dithiole-2-thione, H2C3S5). Solution and solid state NMR spectra have been obtained for selected R(2)Sn(dmit) species as has the crystal structure of MePhSn(dmit) 10. Molecules of 10 in the solid state are linked into zig-zag chains via Sn ... thione S intermolecular associations (Sn-S(5(1)) = 3.139(1) Angstrom; Sn-S(5(1))-C(3(1)) = 111.2(2)degrees). The links between the monomers within the chains are further strengthened by weak S ... S intermonomer interactions, S(5(1)) ... S(2) = 3.315(2) and S(3(1)) ... S(2) = 3.446(2) Angstrom. Furthermore, weaker S ... S interactions (S(5(1)) ... S(1(11)) = 3.635(2) Angstrom) link the chains. The geometry at tin is distorted trigonal bipyramidal; with the equatorial sites occupied by the organic groups (Sn-C = 2.111(5) and 2.134(2) Angstrom) and by a dithiolato sulphur atom (Sn-S(2) = 2.437(1) Angstrom). The axial sites are occupied by the other dithiolato sulphur atom (Sn-S(1) = 2.487(1) Angstrom) and the bridging thione sulphur (S(5(1))): the valency angle, S(5(1))-Sn-S(1), is 161.63(3)degrees with the dithiolate bite angle of 89.92(4)degrees. The R(2)Sn(dmit) compounds react with onium halides, [Q]X to give [Q][R(2)Sn(dmit)X], form complexes, [R(2)Sn(dmit)L], with donors, (e.g. L = bipy, py or DMF), and undergo exchange reactions with R(2)(1)SnCl(2).</p

ORGANOTIN-DMIT COMPLEXES - CRYSTAL-STRUCTURE OF [BU4N][ME2SNCL(DMIT)]

Various organotin-DMIT complexes have been prepared from organotin halides and [Bu4N]2[Ni(DMIT)2] (H2-DMIT = 4,5-dimercapto-1,3-dithiole-2-thione). The crystal structure of [Bu4N][Me2ClSn(DMIT)] (V, R = Me) is reported: the compounds contains a trigonal bipyramidal tin atom in the anion.</p