Intermetallic distances in mercury(I) halides Hg2F2, Hg2Cl2, and Hg2Br2

Dorm, Ebba

doi:10.1039/c29710000466

Cited by 57 publications

(32 citation statements)

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“…The previous correlation of XHg-HgX wavenumbers with the internuclear distances of the metal-metal bond 20 is considered incorrect by Richter et al, 17 based on newer x-ray data of Dorm. 21 The temporal evolution of the Raman signal, following the potential step to anodic regions, was also investigated. Figure 3 shows the surface Raman spectra during mercury oxidation in 0.1 M HCl medium at different times (only the ¾167 cm 1 band is shown).…”

Section: Resultsmentioning

confidence: 99%

In situ micro Raman investigation of electrochemically formed halide and pseudohalide films on mercury electrodes

Brolo

Odziemkowski

Porter

et al. 2002

J Raman Spectroscopy

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Oxidation of pure mercury electrodes was followed by in situ surface-unenhanced Raman spectroscopy. A special spectroelectrochemical cell allowed the observation of spectral features of the oxidation products using a Raman microprobe. The electrochemical behaviour of mercury in basic solution, halide (F − , Cl − , Br − and I − ) and pseudohalide (SCN − ) media was investigated. Insoluble films were formed during the anodic processes in all these systems. The identities of the electrochemically generated films were clearly determined from the Raman spectra. The main product of the electrochemical oxidation of mercury in basic solutions was solid HgO. The anodic behaviour of mercury in the presence of halide yielded insoluble Hg 2 X 2 compounds (where X is the halide). The time dependence of the Raman signals indicated a diffusion-controlled growth of the halide films. The oxidation of mercury in SCN − solutions also produced a solid precipitate [Hg 2 (SCN) 2 ]. Raman bands due to soluble mercury(II) thiocyanate complexes [Hg.SCN/ x 2−x ], present in the electrochemical diffusion layer, were also observed.

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Section: Resultsmentioning

confidence: 99%

In situ micro Raman investigation of electrochemically formed halide and pseudohalide films on mercury electrodes

Brolo

Odziemkowski

Porter

et al. 2002

J Raman Spectroscopy

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“…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).…”

Section: Related Literaturementioning

confidence: 88%

“…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). La structure de ces halogènures a été déterminée au préalable par diffraction des rayons X sur poudre (Havighurst, 1926), puis sur monocristal pour Hg 2 X 2 (X: F, Cl et Br) par Dorm (1970) et pour Hg 2 F 2 par Schrötter & Müller (1992). La structure de Hg 2 I 2 est analogue à celle des autres halogènures, elle est caractérisée par des chaînes linéaires I-Hg-Hg-I le long de l'axe c (Fig.…”

Section: Commentunclassified

Redetermination of Hg₂I₂

et al. 2012

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The crystal structure of mercurous iodide, Hg2I2, has been determined previously from X-ray powder diffraction data [Havighurst (1926 ▶). J. Am. Chem. Soc. 48, 2113–2125]. The results of the current redetermination based on single-crystal X-ray diffraction data provide more precise geometrical data and also anisotropic displacement parameters for the Hg and I atoms, which are both situated on positions with site-symmetry 4mm. The structure consists of linear dimers I—Hg—Hg—I extending along the c axis with an Hg—Hg distance of 2.5903 (13) Å. The overall coordination sphere of the Hg+ atom is a considerably distorted octahedron. The crystal specimen under investigation was twinned by non-merohedry with a refined twin domain fraction of 0.853 (14):0.147 (14).

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“…Although noting that "all the mercurous halides are known to crystallize in molecular lattices of linear X-Hg-Hg-X molecules" [46][47][48], their focus on monomers and dimers avoided the "complications due to crystal-packing forces". Even though the Hg-X bond is polar in the monomer, the "moderately strong covalent bond between the mercury atoms dictates a linear structure (X-Hg-Hg-X) for both fluoride and chloride".…”

Section: Mercurous Halidesmentioning

confidence: 99%

A solid-state 199Hg NMR study of mercury halides

Taylor

Bai

Dybowski

2011

Journal of Molecular Structure

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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.

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Intermetallic distances in mercury(I) halides Hg2F2, Hg2Cl2, and Hg2Br2

Cited by 57 publications

References 0 publications

In situ micro Raman investigation of electrochemically formed halide and pseudohalide films on mercury electrodes

In situ micro Raman investigation of electrochemically formed halide and pseudohalide films on mercury electrodes

Redetermination of Hg₂I₂

A solid-state 199Hg NMR study of mercury halides

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Intermetallic distances in mercury(I) halides Hg2F2, Hg2Cl2, and Hg2Br2

Cited by 57 publications

References 0 publications

In situ micro Raman investigation of electrochemically formed halide and pseudohalide films on mercury electrodes

In situ micro Raman investigation of electrochemically formed halide and pseudohalide films on mercury electrodes

Redetermination of Hg2I2

A solid-state 199Hg NMR study of mercury halides

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Product

Resources

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Redetermination of Hg₂I₂