Structure of solvated mercury(II) halides in liquid ammonia, triethyl phosphite and tri-n-butylphosphine solution

Dalton Transactions : an International Journal of Inorganic Chemistry
Kersti B NilssonM Sandström

Abstract

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(NH(3))(4)](2+), and chloride ions in low concentration, while the lower is a dense highly concentrated solution of [Hg(NH(3))(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 (199)Hg 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 nu(I-Hg-I) symmetric stretching frequency is 132 cm(-1) for the pseudo-tetrahedral [HgI(2)(NH(3))(2)] complex formed in liquid ammonia, corresponding to D(S) = 56 on the donor strength scale. For the Hg(ClO(4))(2)/NH(4)I system in liquid ammonia a (199)Hg NMR study showed [HgI(4)...Continue Reading

References

Jul 15, 1995·Physical Review. B, Condensed Matter·S I ZabinskyM J Eller
Jul 15, 2004·Dalton Transactions : an International Journal of Inorganic Chemistry·Kersti B Nilsson, Ingmar Persson
Apr 27, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Graham A BowmakerGeoffrey B Jameson
Jul 19, 2005·Magnetic Resonance in Chemistry : MRC·Mikhail Maliarik, Ingmar Persson

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Citations

Nov 28, 2013·Inorganic Chemistry·Andreas MetlenRobin D Rogers
Mar 25, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Ulrich SiemelingPetr Štěpnička

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