Synthesis and spectroscopic studies of antimony pentachloride complexes with neutral oxygen, sulfur and selenium ligands

The compounds [SbCl5(R3EY)] (R = Me or Ph; E = P or As; Y = O or S) have been prepared from SbCl5 and the appropriate ligand in CH2Cl2 or CCl4 solutions, and characterised by analysis, IR, 1H, 31P{1H}, 121Sb NMR spectroscopy and conductance measurements. The [SbCl5(μ-L–L)SbCl5] L–L = Ph2P(O)CH2P(O)Ph2, Ph2P(O)(CH2)2P(O)Ph2, Ph2P(S)CH2P(S)Ph2, Ph2As(O)CH2As(O)Ph2, and o-C6H4(P(O)Ph2)2 have been synthesised and similarly characterised. The unstable [SbCl5(R3PSe)] have been prepared at low temperatures and characterised by IR spectroscopy. In solution in chlorocarbons they decompose rapidly to Se and R3PCl2. The reactions of R3SbS with SbCl5 produced R3SbCl2.