- Source: Mercury polycations
Mercury polycations are polyatomic cations that contain only mercury atoms. The best known example is the Hg2+2 ion, found in mercury(I) (mercurous) compounds. The existence of the metal–metal bond in Hg(I) compounds was established using X-ray studies in 1927 and Raman spectroscopy in 1934 making it one of the earliest, if not the first, metal–metal covalent bonds to be characterised.
Other mercury polycations are the linear Hg2+3 and Hg2+4 ions, and the triangular Hg4+3 ion and a number of chain and layer polycations.
Mercury(I)
The best known polycation of mercury is Hg2+2, in which mercury has a formal oxidation state of +1. The Hg2+2 ion was perhaps the first metal-metal bonded species confirmed. The presence of the Hg2+2 ion in solution was shown by Ogg in 1898. In 1900, Baker showed the presence of HgCl dimers in the vapour phase. The presence of Hg2+2 units in the solid state was first determined in 1926 using X-ray diffraction. The presence of the metal-metal bond in solution was confirmed using Raman spectroscopy in 1934.
Hg2+2 is stable in aqueous solution, where it is in equilibrium with Hg2+ and elemental Hg, with Hg2+ present at around 0.6%. Anions of insoluble salts readily shift the equilibrium: S2−, which forms an insoluble Hg(II) salt, induces complete disproportionation, whereas Cl−, which forms an insoluble Hg(I) salt, induces the reverse. Most salts with main group elements tend to contain only Hg(II) and metallic mercury, because the presence of strong Lewis bases destabilizes the intermetallic bond. In appropriate solvents, however, Hg(I) salts with derivatives of amides, pyridines, phosphorus trifluoride, tin(II), and certain other main group elements are all known.
Minerals that are known that contain the Hg2+2 cation include eglestonite.
Linear trimercury and tetramercury cations
Compounds containing the linear Hg2+3 (mercury(2⁄3)) and Hg2+4 (mercury(1⁄2)) cations have been synthesised. These ions are only known in the solid state in compounds such as Hg3(AlCl4)2 and Hg4(AsF6)2. The Hg–Hg bond length is 255 pm in Hg2+3, and 255–262 pm in Hg2+4. The bonding involves 2-centre-2-electron bonds formed by 6s orbitals.
Cyclic mercury cations
The triangular Hg4+3 cation was confirmed in a reinvestigation of the mineral terlinguaite in 1989 and subsequently synthesised in a number of compounds. The bonding has been described in terms of a three-center two-electron bond where overlap of the 6s orbitals on the mercury atoms gives (in D3h symmetry) a bonding "a1" orbital.
Chain and layer polycations
The golden yellow compound Hg2.86(AsF6), named "alchemists' gold" by its discoverers, contains perpendicular chains of Hg atoms.
The "metallic" compounds Hg3NbF6 and Hg3TaF6 contain hexagonal layers of mercury atoms separated by layers of MF−6 anions. They are both superconductors below 7 K.