BISMUTH(III) COMPLEXES WITH SULFUR AND SELENIUM DONOR LIGANDS - SYNTHESIS AND CRYSTAL-STRUCTURES OF BICL3-CENTER-DOT(PR2(N)P(S)P(S)PR2(N) AND [(ME(2)N)(3)PSESEP(NME(2))(3)](2-)() [(BICL4)(2)](N)(2N)

Direct addition of bismuth(III) chloride and tetra-n-propyldiphosphane disulfide gave bright yellow crystals of the 1:1 adduct BiCl3.(Pr2P)- P-n(S)P(S)Pr-2(n). An X-ray crystallographic investigation reveals a h alide-bridged dimeric structure in which each bismuth atom is surround ed by an essentially octahedral arrangement of four chlorine [two term inal, Bi-Cl 2.500(5), 2.516(5), and two bridging, Bi-Cl 2.653(4), 3.01 5(5) Angstrom] and two sulfur atoms [Bi-S 2.857(4), 2.973(4) Angstrom] . Each of the two ligand molecules is involved in bidentate (S,S') che lation to a bismuth atom to form a five-membered ring. Crystals are mo noclinic, space group P2(1)/n, with a = 10.127(6), b = 16.057(6), c = 13.843(6) Angstrom, beta = 93.3(1)degrees, Z = 4, The reaction of BiCl 3 and tris(dimethylamino)phosphane selenide in acetonitrile gave the y ellow crystalline salt [(Me(2)N)(3)PSeSeP(NMe(2))(3)](2+) [(BiCl4)(2)] (2n-)(n) as identified by a crystal structure determination. Formation of the unusual cation follows from air oxidation of the organophosphi ne selenide in the presence of BiCl3. The Se-Se bond distance is 2.309 (5) Angstrom and the torsion angle P-Se-Se-P is -112.4(4)degrees. For the anion, linkage of dimeric (BiCl4), units via further halide bridgi ng results in an infinite chain structure of edge-shared octahedra. Cr ystals are triclinic, space group P (1) over bar with a = 7.386(6), b = 12.813(8), c = 18.919(8) Angstrom, alpha = 76.0(1), beta = 78:9(1), gamma = 73.2(1)degrees and Z = 2.