New mono and binuclear mercury(II) complexes of phosphorus ylides containing DMSO as ligand: Spectral and structural characterization

Reaction of phosphorus ylides Ph3PCHC(O)C6H4NO2 (Y′) and (p-tolyl)3PCHC(O)C6H4Cl (Y″) with HgX2 (X = Cl, Br and I) in equimolar ratios using methanol as solvent leads to binuclear products. The bridge-splitting reaction of binuclear complex [(Y″) · HgI2]2 by DMSO yields the mononuclear complex [(Y″) · HgI2 · DMSO]. This bridge-splitting reaction can be also a method for the synthesis of mononuclear products. C-coordination of ylides and O-coordination of DMSO are demonstrated by single crystal X-ray analyses of binuclear complexes of [(Y′) · HgI2]2 and [(Y″) · HgI2]2 and mononuclear complex of [(Y″) · HgI2 · DMSO]. Characterization of the obtained compounds was also performed by elemental analysis, IR, 1H, 31P, and 13C NMR. Theoretical studies on Hg(II) complexes of Y′ show that the cis-like isomers are about 4–12 kcal/mol less stable than the trans-like structures and the relative energy of cis- and trans-like isomers significantly depends on the size of the bridging halide. These studies on mercury complexes of Y″ show that, formation of mononuclear complexes in DMSO solution in which DMSO acts as a ligand, energetically is more favorable than that of binuclear complexes.