Structural, theoretical and multinuclear NMR study of mercury(II) complexes with a new ambidentate phosphorus ylide

Abstract

The reaction of the new ambidentate ylide, Ph 3PCHCOCH 2COOC 2H 5 (EAPPY), with HgX 2 (X = Cl, Br and I) in equimolar ratios using methanol as the solvent leads to binuclear complexes of the type [EAPPY·HgX 2] 2 (X = Cl ( 1), Br ( 2) and I ( 3)). Single crystal X-ray analysis reveals the presence of a centrosymmetric dimeric structure containing the ylide and HgX 2 (X = Br or I) . The IR and NMR data of the product [(EAPPY)·HgCl 2] 2 ( 1), formed by the reaction of mercury(II) chloride with the same ylide, are similar to those of 2 and 3. Analytical data indicate a 1:1 stoichiometry between the ylide and Hg(II) halide in each of the three products. Theoretical studies indicate that the nature of the R group in ylides of the type Ph 3PCHCOR has a weak effect on the Hg–C(ylide) bond length in binuclear Hg 2L 2I 4 complexes.