Liquid ammonia, trialkyl phosphites, and especially trialkylphosphines, are very powerful electron-pair donor solvents with soft bonding character. The solvent molecules act as strongly coordinating ligands towards mercury(II), interacting strongly enough to displace halide ligands. In liquid ammonia mercury(II) chloride solutions separate into two liquid phases; the upper contains tetraamminemercury(II) complexes, [Hg(NH₃)₄]²⁺, and chloride ions in low concentration, while the lower is a dense highly concentrated solution of [Hg(NH₃)₄]²⁺ entities, ca. 1.4 mol dm⁻³, probably ion-paired by hydrogen bonds to the chloride ions. Mercury(II) bromide also dissociates to ionic complexes in liquid ammonia and forms a homogeneous solution for which ¹⁹⁹Hg NMR indicates weak bromide association with mercury(II). When dissolving mercury(II) iodide in liquid ammonia and triethyl phosphite solvated molecular complexes form in the solutions. The Raman ν(I–Hg–I) symmetric stretching frequency is 132 cm⁻¹ for the pseudo-tetrahedral [HgI₂(NH₃)₂] complex formed in liquid ammonia, corresponding to D_S = 56 on the donor strength scale. For the Hg(ClO₄)₂/NH₄I system in liquid ammonia a ¹⁹⁹Hg NMR study showed [HgI₄]²⁻ to be the dominating mercury(II) complex for mole ratios n(I⁻) : n(Hg²⁺) ≥ 6. A large angle X-ray scattering (LAXS) study of mercury(II) iodide in triethyl phosphite solution showed a [HgI₂(P(OC₄H₉)₃)₂] complex with the Hg–I and Hg–P bond distances 2.750(3) and 2.457(4) Å, respectively, in near tetrahedral configuration. Trialkylphosphines generally form very strong bonds to mercury(II), dissociating all mercury(II) halides. Mercury(II) chloride and bromide form solid solvated mercury(II) halide salts when treated with tri-n-butylphosphine, because of the low permittivity of the solvent. A LAXS study of a melt of mercury(II) iodide in tri-n-butylphosphine at 330 K resulted in the Hg–I and Hg–P distances 2.851(3) and 2.468(4) Å, respectively. The absence of a distinct I–I distance indicates flexible coordination geometry with weak and non-directional mercury(II) iodide association within the tri-n-butylphosphine solvated complex.