Synthesis and characterization of binuclear mercury(II) complexes of phosphorus ylides, X-ray analysis and multinuclear NMR measurements

The reactions of phosphorus ylide (p-tolyl)3PCHC(O)CH3 (Y1) with HgX2 (X = Cl and Br) and (p-tolyl)3PCHC(O)C6H4NO2 (Y2) with HgX2 (X = Cl, Br and I) in equimolar ratios using methanol as a solvent are reported. These reactions led to binuclear complexes. C-Coordination of ylides and trans-like structure of complexes [(Y1) · HgBr2]2 and [(Y2) · HgBr2]2 · 2DMSO are demonstrated by single crystal X-ray analyses. The IR, 1H, 13C and 31P NMR data for the other synthesized compounds are similar to the latter complexes, indicating similar structures. Elemental analyses indicate a 1:1 stoichiometry between the ylide and Hg(II) halide in all the products. The ab initio studies indicated that for all dimeric compounds, the observed trans-like structures are 7–10 kcal/mol more stable than the alternative possible cis-like isomers. Although the calculated bond lengths are slightly longer than the measured ones, the similarity of calculated and measured bond angles reflects the similar geometrical structures for these compounds in both the solid state and the gas phase.