A solid-state 199Hg NMR study of mercury halides

Abstract

Abstract:The principal elements of the 199 Hg chemical-shift (CS) tensors of the mercuric halides (HgX 2 , X = F, Cl, Br, and I) and the mercurous halides (Hg 2 X 2 , X = F and Cl) were determined from spectra of static polycrystalline powders and from magic-angle spinning (MAS) spectra. The CS tensors of both HgCl 2 and Hg 2 Cl 2 are axially symmetric (η = 0) within experimental error, differing from literature reports of η=0.12 and η=0.14, respectively. The principal elements of the axially symmetric CS tensor in HgBr 2 were also measured using a static sample, and the wideline spectra of HgF 2 and HgI 2 (red polymorph) give chemical-shift tensors that suggest, within experimental error, that the mercury sits in sites of cubic symmetry. The 199 Hg CS tensor for Hg 2 F 2 is asymmetric.Experiments with static polycrystalline samples may allow the determination of the elements of the 199 Hg CS tensors even when MAS fails to completely average the dipolar coupling of the spin-½ 199 Hg and the quadrupolar halide nucleus.

An ionic liquid process for mercury removal from natural gas

“…For χ CuCl 2 = 0.33, this peak was found at −1106 ppm (relative to 1 M HgCl 2 in dmso); for χ CuCl 2 = 0.50, the peak appeared at −1140 ppm. These positions are consistent with the formation of chloromercurate(II) anions, 37 where the mercury is in the environment of four chlorine atoms. The lower field peak is assigned to [HgCl 4 ] 2− and the higher peak to [Hg 2 Cl 6 ] 2− .…”

Preparation of RHgCl via transmetalation of (8-quinolyl)SnMe3and redistribution to R2Hg (R = 8-quinolyl): a highly distorted diorganomercury(ii) with 84 degree C–Hg–C angle

“…1 H NMR spectra were referenced to the solvent residual peak (CDCl 3 , δ 7.24 ppm; CD 3 CN, δ 1.94 ppm; DMSO-d6, δ 2.50 ppm; pyridine-d5, δ 8.74 ppm). 13 C NMR spectra were referenced to the solvent residual peak (CDCl 3 , δ 77.0 ppm; DMSO-d6, δ 39.0 ppm; pyridine-d5, δ 150.4 ppm; CD 3 CN, δ 118.2 ppm). 199 Hg NMR was calibrated using 1 M HgCl 2 and 1 M HgI 2 as external standards.…”

“…199 Hg NMR was calibrated using 1 M HgCl 2 and 1 M HgI 2 as external standards. 13 [Caution! DMSO is readily absorbed through the skin.…”

Redetermination of Hg2I2

“…Studies based on single crystals for X = F, Cl, Br were reported by Dorm (1970) and for X = F also by Grdenić & Djordjević (1956) and Schrö tter & Mü ller (1992). For the physical properties of mercurous halides, see: Zadokhin & Solodovnik (2004); Markov et al (2007Markov et al ( , 2010; Taylor et al (2011). For theoretical studies of the structures of mercurous halides, see: Liao & Zhang (1995); Liao & Schwarz (1997 Table 1 Selected bond lengths (Å ).…”

“…Ces dernières années, ces composés ont fait l'objet de nombreux travaux, essentiellement pour leurs propriétés dynamiques (Zadokhin & Solodovnik, 2004), ferroélastiques (Markov et al 2007(Markov et al , 2010 et résonnances magnétiques nucléaires (NMR) (Taylor et al, 2011). La présence de liaisons Hg-Hg, qui est l'une des caractéristiques de ce type de composé a suscité plusieurs études quant à la nature et aux propriétés de ces liaisons (Liao & Zhang, 1995;Liao & Schwarz, 1997).…”