Vibrational spectra of mercury(I) nitrate in aqueous solution and of the crystalline hydrolysis products

Abstract

Aqueous solutions of 'mercurous nitrate' are shown by Raman spectra to contain the complexes [Hg2(OH2)NO3]+ and [Hg2(OH2)2]2+. Crystalline dimercury(I) nitrate, Hg2(NO3)2,2H2O, and its solid hydrolysis products Hg2(OH)2,3Hg2(NO3)2, 2Hg2(OH)2,3Hg2(NO3)2,H2O and Hg2(OH)2,- Hg2(NO3)2 have been obtained: the vibrational spectra are reported and interpreted in terms of possible structures. Modes v(Hg-Hg) appear in the range 170- 200 cm-1 and are sensitive to the particular combination of the ligands OH, ONO2, and H2O attached to the dimercury(I) ion.

Structural study of the system Hg2O–N2O5–H2O; crystal structures of three basic mercury(I) nitrates – hydrolysis products of mercury(I) nitrate dihydrate

“…Forty-five years later, by the analysis of the vibrational spectra of mercurous nitrate dihydrate and its hydrolysis products, Tan & Taylor (1978) confirmed the existence of only three 'basic' mercurous nitrates. * Tan & Taylor were able to identify the functional groups but left solution of the structure to X-ray crystallography.…”

“…The crystals of (1), (2) and (3) were prepared as described by Tan & Taylor (1978). Density was measured pycnometrically in CC14.…”

Linkage Scrambling in Branched Chain Polymercury Compounds: Nitrides from the Mercury‐Mediated Disproportionation of N2O3

“…Yet mercury's chemistry remains enigmatic; even its simplest manifestations, such as its low metallic phase melting point, require sophisticated theory involving relativistic effects to fully unmask. Metal salts of hard anions, such as oxygen and nitrogen, are not normally complicated, but with mercury they are structurally diverse, with a penchant for covalently linked chain and layered structures The oxidation state of mercury is often the key structural determinant, and stark differences are found in coordination and bonding for the mercuric(II) and mercurous(I) salts. Mercuric oxide, HgO, is a well‐known red‐to‐yellow compound that forms a robust orthorhombic phase with zigzag planar chains.…”

“…[6] Finally, the nitrides of mercury form a diverse range of compounds which are an intersection of solid state and covalent network structures. [7] Valiant attempts have been made to sort out this morass, particularly with the aid of vibrational spectroscopy, [3] and some systemization has resulted from the crystallographic characterization of several key products from the hydrolysis condensation. [8,9] However, it is clear that although this area is easily accessed through hydrolytic reactions, there remain problems with product isolation and identification; deficiencies in our understanding of this chemistry remain as glaring as they were a century ago.…”

“…We have recently found an alternative entrance to this complex manifold of chemistry, one that gives cleaner, reproducible yields of a nitride-based solid which was previously formulated as a hydroxide species, [HOHg 4 ] +3 (NO 3 -1 ) 3 . We propose that the nitride and "hydroxide" phases are isostructural, and that indeed some preparations may generate mixed phases of hydroxide and nitride.…”