Add time:08/01/2019         Source:sciencedirect.com

The preparation of complexes of the type HgX2(PR3)2 [X = Cl, Br or I; R = 2-furyl or 2-thienyl] has been investigated, and a series of compounds has been characterised by analytical and, where possible, solid state vibrational and 31P NMR solution studies. In addition, the X-ray crystal structure of HgCl2[P(2-thienyl)3]2 has been determined. Crystals of the complex are monoclinic, space group P21/n, with a = 9.556(6), b = 18.280(10), c = 16.609(9) Å, β = 102.14(5)°. The structure was solved using the heavy atom method and refined to a final R-value of 0.049 for 4067 observed diffractometer data. The complex is found to be a distorted tetrahedral monomer, and the geometry about mercury has been compared with that found in HgCl2(PR3)2 (R = Et or Ph). These data, and in particular, the relative values of the PHgP angle, indicate the σ-donating ability of tri(2-thienyl)phosphine to be substantially weaker than that of triethylphosphine. Comparison of 1J(199Hg31P) coupling constants indicates that both triheteroarylphosphines are weaker σ-donors towards mercury(II) halides than is triphenylphosphine, a view given support by the crystallographic data, and also by the solid state vibrational data for certain of the complexes.

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