Syntheses and NMR-Studies of Cationic Mercury Xanthate, Dithiophosphate and Dithiocarbamate Tricyclohexylphosphine Adducts - the Crystal and Molecular-Structures of [Hg(S2cnet2)(P(C-C6h11)3)2]+ (Cf3so3)- [Hg(S2copri)(P(C-C6h11)3)2]+ (Clo4)-.ch2cl2 And [Hg(S2p(Opri)2)(P(C-C6h11)3)2]+ (Cf3so3)-

Abstract

Phosphorus-31 and mercury-199 N.M.R . data are presented for the phosphine adducts Hg(S-S)(P(c-C₆H₁₁)₃) nA (S-S = isopropylxanthate ( ipxan ), diisopropyl dithiophosphate ( dipdtp ), diethyldithiocarbamate ( dedtc ); n = 1,2; A = CF₃SO₃, ClO₄, S-S). When A = CF₃SO₃, ClO₄ and n = 1 or 2, the cationic species [Hg(S-S)P(c-C₆H₁₁)₃]⁺ and [Hg(S-S)(P(c- C₆H₁₁)₃)₂]⁺ respectively are formed in which the S-S ligands act as bidentate donors. When A = S-S and n = 2 there is rapid exchange between the S-S ligands with the complexes remaining four-coordinate, even at low temperature. The position of the dithiophosphate phosphorus-31 resonance for compounds with S-S = dipdtp , reveals whether the dipdtp ligand acts as a monodentate or bidentate donor in solution.     The crystal structures of Hg( dedtc )(P(c-C₆H₁₁)₃)₂(CF₃SO₃), Hg( ipxan )(P(c-C₆H₁₁)₃)₂(ClO₄).CH₂Cl₂ and Hg( dipdtp )(P(c-C₆H₁₁)₃)₂(CF₃SO₃) have been determined. Crystals of Hg( dedtc )(P(c-C₆H₁₁)₃)₂(CF₃SO₃) are monoclinic, P2₁/c, a 11.100(3), b 31.508(7), c 14.998(2)Ǻ, β 111.05(2)° Z 4. Crystals of Hg ( ipxan )(P(c-C₆H₁₁)₃)₂ClO₄.CH₂Cl₂ are triclinic, Pī , a 13.604(5), b 13.734(3) c 14.666(5)Ǻ α 77.74(2)°,β 65.68(3)°, y 80.40(2)°, Z 2. Crystals of Hg( dipdtp )(P(c-C₆H₁₁)₃)₂(CF₃SO₃) are monoclinic, P2₁/c, a 10.440(2), b 22.615(4), c 21.904(3),β 93.05(1)°, Z 4. The observed deviation from the expected tetrahedral environment of the mercury atom is discussed on the basis of ligand bite and steric requirements.