The Lewis-base behavior of Bunsen’s cacodyl disulfide, Me₂As(S)–S–AsMe₂, toward molecular halides of group 13

Article type: Research Article

Authors: Ioannou, Panayiotis V. | Tsivgoulis, Gerasimos M. | Vachliotis, Dimitris G.

Affiliations: Department of Chemistry, University of Patras, Patras, Greece

Note: [] Corresponding author. Email: ioannou@chemistry.upatras.gr

Note: [] Corresponding author. Email: tsivgoulis@chemistry.upatras.gr

Abstract: Molecular halides of group 13 in chloroform solutions interact but do not split Bunsen’s cacodyl disulfide, Me2As(S)–S–AsMe2. With BF3·Et2O cacodyl disulfide gives an equilibrated mixture of Me2As(S)–S–AsMe2 and Me2As–SS–AsMe2, whereas AlCl3 causes complete isomerization to Me2As–SS–AsMe2 which is stabilized by complexation to AlCl3. GaCl3 and InCl3 do not isomerize Me2As(S)–S–AsMe2 but only bind to it. Thallium(III) acetate, splits Me2As(S)–S–AsMe2 giving initially the unstable thallium(III) complex, (Me2AsS2)3Tl, which is spontaneously converted to Me2AsS2Tl. The electrons for the reduction Tl(III)→Tl(I) most likely come from two of the –S:− sulfur anions bound to the initially formed (Me2AsS2)3Tl.

Keywords: dimethylarsino dimethyldithioarsinate, boron trifluoride etherate, aluminum(III), gallium(III), indium(III) chlorides, thallium(III) acetate, thallium(I) dimethyldithioarsinate

DOI: 10.1080/10241220903015800

Journal: Main Group Chemistry, vol. 8, no. 3, pp. 151-161, 2009