X-Ray Crystal and Molecular Structures of di-iodomercury(II) and dichloromercury(II)

Article abstract of DOI:10.1039/DT9900000691

Reaction of mercury(II) iodide with the unsymmetrical diphosphine ligand Ph2P(S)CH2PPh2 resulted in the formation of a solid compound > (1), which has been shown by X-ray crystallography to be monomeric with a flattened tetrahedral geometry about the mercury atom.The diphosphine co-ordinates via the sulphur and trivalent phosphorus atoms forming a five-membered ring; the two remaining tetrahedral sites are occupied by the iodide atoms .Crystals of (1) are monoclinic, space group P2₁/c, with unit-cell dimensions a = 11.426(2), b = 15.491(4), c = 16.324(3) Angstroem, β = 109.79(1), and Z = 4.The structure was refined to final R = 0.059 for 2632 reflections with I >= 3.0?(I).The reaction of mercury(II) chloride with the symmetrical diphosphine Ph2P(S)CH2CH2(S)PPh2 led to the isolation of the adduct > (2).Crystallographic studies revealed a distorted tetrahedral mercury centre defined by two chloride atoms and a chelating diphosphine ligand which co-ordinates via the sulphur atoms .The mode of co-ordination of the diphosphine ligand results in the formation of a seven-membered ring, a result which is unprecedented in phosphine/arsine chalcogenide chemistry.Crystals of (2) are monoclinic, space group P2₁/n, with unit-cell dimensions a = 8.404(4), b = 16.829(3), c = 19.354(3) Angstroem, β= 91.02(3), and Z = 4.The structure was refined to final R = 0.056 for 3406 reflections with I >= 2.5?(I).

Full text of DOI:10.1039/DT9900000691

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