Multinuclear NMR Spectroscopic and X-ray Crystallographic Studies of a Series of Mercury(II) Complexes Containing the Bidentate Phosphine Ligand Ph(2)PCH(2)Si(CH(3))(2)CH(2)PPh(2) (L(2)).
The bidentate phosphine ligand Ph(2)PCH(2)Si(CH(3))(2)CH(2)PPh(2) (L(2)), an analogue of 1,3-bis(diphenylphosphino)propane (dppp), coordinates to mercury(II) salts to form complexes of the general formula [HgX(2).L(2)] (X = Cl, Br, I, NCS). Infrared, Raman, and multinuclear ((1)H, (13)C, (31)P, (199)Hg) NMR spectroscopic studies show that the complexes exhibit four-coordinate pseudotetrahedral metal geometry. [HgI(2)(Ph(2)PCH(2)Si(CH(3))(2)CH(2)PPh(2))] (1) crystallizes in the monoclinic space group P2(1)/n with a = 13.028(2) Å, b = 17.402(5) Å, c = 13.849(2) Å, beta = 90.635(14) degrees, V = 3139.5(11) Å(3), and Z = 4. The structure contains a tetrahedral mercury center with the phosphine ligand bound in a bidentate fashion: Hg-P 2.511(2), 2.515(2) Å; P-Hg-P 105.28(6) degrees. The complex [HgCl(2)](2).L(2) has also been generated via a 2:1 metal:phosphine stoichiometry.
Alyea
Elmer C.
EC
Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ontario, Canada N1G 2W1.
Ferguson
George
G
Shakya
Ram P.
RP
Meehan
Paul R.
PR