Bismuth(III) complexes with sulfur and selenium donor ligands: synthesis and crystal structures of BiCl3·Prn2P(S)P(S)Prn2 and [(Me2N)3PSeSeP(NMe2)3]2+[(BiCl4)2]n2n–

Abstract

Direct addition of bismuth(III) chloride and tetra-n-propyldiphosphane disulfide gave bright yellow crystals of the 1 : 1 adduct BiCl₃·Prⁿ₂P(S)P(S)Prⁿ₂. An X-ray crystallographic investigation reveals a halide-bridged dimeric structure in which each bismuth atom is surrounded by an essentially octahedral arrangement of four chlorine [two terminal. Bi–Cl 2.500(5), 2.516(5), and two bridging, Bi–Cl 2.653(4). 3.015(5)Å] and two sulfur atoms [Bi–S 2.857(4), 2.973(4)Å]. Each of the two ligand molecules is involved in bidentate (S,S′) chelation to a bismuth atom to form a five-membered ring. Crystals are monoclinic, space group P2₁n, with a= 10.127(6), b= 16.057(6), c= 13.843(6)Å, β= 93.3(1)°, Z= 4. The reaction of BiCl₃and tris(dimethylamino)phosphane selenide in acetonitrile gave the yellow crystalline salt [(Me₂N)₃PSeSeP(NMe₂)₃]²⁺[(BiCl₄)₂]_n^2n– as identified by a crystal structure determination. Formation of the unusual cation follows from air oxidation of the organophosphine selenide in the presence of BiCl₃. The Se–Se bond distance is 2.309(5)Å and the torsion angle P–Se–Se–P is –112.4(4)°. For the anion, linkage of dimeric (BiCl₄)2 units via further halide bridging results in an infinite chain structure of edge-shared octahedra. Crystals are triclinic, space group P with a= 7.386(6), b= 12.813(8), c = 18.919(8)Å, α= 76.0(1 ), β= 78.9(1 ), γ= 73.2(1)° and Z= 2.