Reactivity of diphosphines towards methyl- and phenyl-mercury(II) ions. Crystal structure of [Hg(Ph(2)PCH(2)CH(2)PPh(2))(2)][O3(S)CF(3)](2)

Methyl- and phenyl-mercury(II) ions reacted, in the molar ratio 2:1, with bidentate phosphines L-L to give binuclear complexes of general formula [RHg(L-L)HgR](2+).[L-L = Ph(2)P(CH2)(n)PPh(2), n = 1-3]. When an excess of the phosphine ligand is present an intermolecular exchange process occurs which leads to the formation of the symmetrically substituted compounds, HgR(2) and [Hg(L-L)(2)](2+). The reactions in solution have been studied by multinuclear NMR spectroscopy; the structure of the bimetallic species was deduced with the aid of computer simulation. The single-crystal structure of [Hg(Ph(2)PCH(2)CH(2)PPh(2))(2)][O3SCF3](2) [orthorhombic, space group Pbcn, a = 17.141(3), b = 20.158(3), c = 15.614(9) Angstrom, Z = 4] showed the mercury atom to be in a distorted-tetrahedral configuration.