Mercury(II) hydride

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Mercury(II) hydride
Computed-structure-of-HgH2.png
Names
IUPAC name
Mercury(II) hydride
Other names
Mercurane
Mercuric hydride
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/Hg.2H
    Key: JUQLLZUJMFHASM-UHFFFAOYSA-N
  • [H][Hg][H]
Properties
HgH
2
Molar mass 202.61 g mol−1
Related compounds
Related compounds
Zinc hydride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Mercury(II) hydride (systematically named mercurane(2) and dihydridomercury) is an inorganic compound with the chemical formula HgH
2
(also written as [HgH
2
]
). It is both thermodynamically and kinetically unstable at ambient temperature, and as such, little is known about its bulk properties. However, it can also be a white, crystalline solid, which is kinetically stable at temperatures below −125 °C (−193 °F), which was synthesized for the first time in 1951. [1]

Contents

Mercury(II) hydride is the second simplest mercury hydride (after the significantly less stable mercury(I) hydride). Due to its instability, it has no practical industrial uses. However, in analytical chemistry, mercury(II) hydride is fundamental to certain forms of spectrometric techniques used to determine mercury content. In addition, it is investigated for its effect on high sensitivity isotope-ratio mass spectrometry methods that involve mercury, such as MC-ICP-MS, when used to compare thallium to mercury. [2]

Properties

Structure

In solid mercury(II) hydride, the HgH2 molecules are connected by mercurophilic bonds. Trimers and a lesser proportion of dimers are detected in the vapour. Unlike solid zinc(II), and cadmium(II) hydride, which are network solids, solid mercury(II) hydride is a covalently bound molecular solid. This is due to relativistic effects, which also accounts for the relatively low decomposition temperature of -125 °C. [3]

The HgH2 molecule is linear and symmetric in the form H-Hg-H. The bond length is 1.646543 Å. The antisymmetric stretching frequency, ν3 of the bond is 1912.8 cm−1, 57.34473 THz for isotopes 202Hg and 1H. [3] The energy needed to break the Hg-H bond in HgH2 is 70 kcal/mol. The second bond in the resulting HgH is much weaker only needing 8.6 kcal/mol to break. Reacting two hydrogen atoms releases 103.3 kcal/mol, and so HgH2 formation from hydrogen molecules and Hg gas is endothermic at 24.2 kcal/mol. [3]

Biochemistry

Alireza Shayesteh et al conjectured that bacteria containing the flavoprotein mercuric reductase, such as Escherichia coli , can in theory reduce soluble mercury compounds to volatile HgH2, which should have a transient existence in nature.

Production

Mercury(II) chloride reduction

Mercury(II) hydride may be prepared by the reduction of mercury(II) chloride. In this process, mercury(II) chloride and a hydride salt equivalent react to produce mercury(II) hydride according to the following equations, which depend on the stoichiometry of the reaction:

2 HgCl
2
+ 2 H
HgCl2−
4
+ HgH
2
HgCl
2
+ 2 H
HgH
2
+ 2 Cl

Variations of this method exits where mercury(II) chloride is substituted for its heavier halide homologues.

Direct synthesis

Mercury(II) hydride can also be generated by direct synthesis from the elements in the gas phase or in cryogenic inert gas martices: [3]

Hg → Hg*
Hg* + H
2
→ [HgH
2
]*
[HgH
2
]*HgH
2

This requires excitation of the mercury atom to the 1P or 3P state, as atomic mercury in its ground-state does not insert into the dihydrogen bond. [3] Excitation is accomplished by means of an ultraviolet-laser, [1] or electric discharge. [3] The initial yield is high; however, due to the product being in an excited state, a significant amount dissociates rapidly into mercury(I) hydride, then back into the initial reagents:

2 [HgH
2
]* → 2 HgH + H
2
2 HgH → Hg
2
H
2
Hg
2
H
2
→ 2 Hg + H
2

This is the preferred method for matrix isolation research. Besides mercury(II) hydride, it also produces other mercury hydrides in lesser quantities, such as the mercury(I) hydrides (HgH and Hg2H2).

Reactions

Upon treatment with a Lewis base, mercury(II) hydride converts to an adduct. Upon treatment with a standard acid, mercury(II) hydride and its adducts convert either to a mercury salt or a mercuran(2)yl derivative and elemental hydrogen.[ citation needed ] Oxidation of mercury(II) hydride gives elemental mercury.[ citation needed ] Unless cooled below −125 °C (−193 °F), mercury(II) hydride decomposes to produce elemental mercury and hydrogen: [4]

HgH
2
→ Hg + H2

History

Mercury(II) hydride was successfully synthesized and identified in 1951 by Egon Wiberg and Walter Henle, by the reaction of mercury(II) iodide and lithium tetrahydroaluminate in a mixture of petroleum ether and tetrahydrofuran. In 1993 Legay-Sommaire announced HgH2 production in cryogenic argon and krypton matrices with a KrF laser. [1] In 2004, solid HgH2 was definitively synthesized and consequentially analysed, by Xuefeng Wang and Lester Andrews, by direct matrix isolation reaction of excited mercury with molecular hydrogen. [4] In 2005, gaseous HgH2 was synthesized by Alireza Shayesteh et al, by the direct gas-phase reaction of excited mercury with molecular hydrogen at standard temperature; [5] and Xuefeng Wang and Lester Andrews [4] determined the structure of solid mercury HgH2, to be a molecular solid.

Related Research Articles

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H), a hydrogen atom with two electrons. In modern usage, this is typically only used for ionic bonds, but it is sometimes (and more frequently in the past) been applied to all compounds containing covalently bound H atoms. In this broad and potentially archaic sense, water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. In covalent compounds, it implies hydrogen is attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

<span class="mw-page-title-main">Hydrogenation</span> Chemical reaction between molecular hydrogen and another compound or element

Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organic compounds. Hydrogenation typically constitutes the addition of pairs of hydrogen atoms to a molecule, often an alkene. Catalysts are required for the reaction to be usable; non-catalytic hydrogenation takes place only at very high temperatures. Hydrogenation reduces double and triple bonds in hydrocarbons.

Borderline hydrides typically refer to hydrides formed of hydrogen and elements of the periodic table in group 11 and group 12 and indium (In) and thallium (Tl). These compounds have properties intermediate between covalent hydrides and saline hydrides. Hydrides are chemical compounds that contain a metal and hydrogen acting as a negative ion.

<span class="mw-page-title-main">Aluminium hydride</span> Chemical compound

Aluminium hydride is an inorganic compound with the formula AlH3. Alane and its derivatives are part of a family of common reducing reagents in organic synthesis based around group 13 hydrides. In solution—typically in ethereal solvents such tetrahydrofuran or diethyl ether—aluminium hydride forms complexes with Lewis bases, and reacts selectively with particular organic functional groups, and although it is not a reagent of choice, it can react with carbon-carbon multiple bonds. Given its density, and with hydrogen content on the order of 10% by weight, some forms of alane are, as of 2016, active candidates for storing hydrogen and so for power generation in fuel cell applications, including electric vehicles. As of 2006 it was noted that further research was required to identify an efficient, economical way to reverse the process, regenerating alane from spent aluminium product.

<span class="mw-page-title-main">Plumbane</span> Chemical compound

Plumbane is an inorganic chemical compound with the chemical formula PbH4. It is a colorless gas. It is a metal hydride and group 14 hydride composed of lead and hydrogen. Plumbane is not well characterized or well known, and it is thermodynamically unstable with respect to the loss of a hydrogen atom. Derivatives of plumbane include lead tetrafluoride, PbF4, and tetraethyllead, (CH3CH2)4Pb.

Transition metal hydrides are chemical compounds containing a transition metal bonded to hydrogen. Most transition metals form hydride complexes and some are significant in various catalytic and synthetic reactions. The term "hydride" is used loosely: some of them are acidic (e.g., H2Fe(CO)4), whereas some others are hydridic, having H-like character (e.g., ZnH2).

<span class="mw-page-title-main">Beryllium hydride</span> Chemical compound

Beryllium hydride is an inorganic compound with the chemical formula n. This alkaline earth hydride is a colourless solid that is insoluble in solvents that do not decompose it. Unlike the ionically bonded hydrides of the heavier Group 2 elements, beryllium hydride is covalently bonded.

Zinc hydride is an inorganic compound with the chemical formula ZnH2. It is a white, odourless solid which slowly decomposes into its elements at room temperature; despite this it is the most stable of the binary first row transition metal hydrides. A variety of coordination compounds containing Zn–H bonds are used as reducing agents, but ZnH2 itself has no common applications.

Binary compounds of hydrogen are binary chemical compounds containing just hydrogen and one other chemical element. By convention all binary hydrogen compounds are called hydrides even when the hydrogen atom in it is not an anion. These hydrogen compounds can be grouped into several types.

Cadmium hydride is an inorganic compound with the chemical formula (CdH
2
)
n
. It is a solid, known only as a thermally unstable, insoluble white powder.

Mercury(I) hydride is an inorganic compound with the chemical formula HgH. It has not yet been obtained in bulk, hence its bulk properties remain unknown. However, molecular mercury(I) hydrides with the formulae HgH and Hg
2
H
2
have been isolated in solid gas matrices. The molecular hydrides are very unstable toward thermal decomposition. As such the compound is not well characterised, although many of its properties have been calculated via computational chemistry.

Titanium(IV) hydride is an inorganic compound with the empirical chemical formula TiH
4
. It has not yet been obtained in bulk, hence its bulk properties remain unknown. However, molecular titanium(IV) hydride has been isolated in solid gas matrices. The molecular form is a colourless gas, and very unstable toward thermal decomposition. As such the compound is not well characterised, although many of its properties have been calculated via computational chemistry.

<span class="mw-page-title-main">Chromium(I) hydride</span> Chemical compound

Chromium(I) hydride, systematically named chromium hydride, is an inorganic compound with the chemical formula (CrH)
n
. It occurs naturally in some kinds of stars where it has been detected by its spectrum. However, molecular chromium(I) hydride with the formula CrH has been isolated in solid gas matrices. The molecular hydride is very reactive. As such the compound is not well characterised, although many of its properties have been calculated via computational chemistry.

Chromium(II) hydride, systematically named chromium dihydride and poly­(dihydridochromium) is pale brown solid inorganic compound with the chemical formula (CrH2)n. Although it is thermodynamically unstable toward decomposition at ambient temperatures, it is kinetically metastable.

Iron(II) hydride, systematically named iron dihydride and poly(dihydridoiron) is solid inorganic compound with the chemical formula (FeH
2
)
n
(also written ([FeH
2
]
)n or FeH
2
). ). It is kinetically unstable at ambient temperature, and as such, little is known about its bulk properties. However, it is known as a black, amorphous powder, which was synthesised for the first time in 2014.

<span class="mw-page-title-main">Chlorobis(dppe)iron hydride</span> Chemical compound

Chlorobis(dppe)iron hydride is a coordination complex with the formula HFeCl(dppe)2, where dppe is the bidentate ligand 1,2-bis(diphenylphosphino)ethane. It is a red-violet solid. The compound has attracted much attention as a precursor to dihydrogen complexes.

<span class="mw-page-title-main">Magnesium monohydride</span> Chemical compound

Magnesium monohydride is a molecular gas with formula MgH that exists at high temperatures, such as the atmospheres of the Sun and stars. It was originally known as magnesium hydride, although that name is now more commonly used when referring to the similar chemical magnesium dihydride.

Barium hydride is a chemical compound with the chemical formula BaH2.

Germyl, trihydridogermanate(1-), trihydrogermanide, trihydridogermyl or according to IUPAC Red Book: germanide is an anion containing germanium bounded with three hydrogens, with formula GeH−3. Germyl is the IUPAC term for the –GeH3 group. For less electropositive elements the bond can be considered covalent rather than ionic as "germanide" indicates. Germanide is the base for germane when it loses a proton.

<span class="mw-page-title-main">Tetrakis(trimethylphosphine)tungsten(II) trimethylphospinate hydride</span> Chemical compound

Tetrakis(trimethylphosphine)tungsten(II) trimethylphospinate hydride (W(PMe3)42-CH2PMe2)H) is an air-sensitive organotungsten complex with tungsten in the oxidation state of +2. It is an electron-rich tungsten center is and, thus, prone to oxidation. This bright-yellow complex has been used as a starting retron for some challenging chemistry, such as C-C bond activation, tungsten-chalcogenide multiple bonding, tungsten-tetrel multiple bonding, and desulfurization.

References

  1. 1 2 3 Legay-Sommaire, N.; F. Legay (1993). "Photochemistry in Hg doped matrices. Infrared spectra of mercury hydrides: HgH2, HgD2, HHgD, HgD". Chemical Physics Letters. 207 (2–3): 123–128. Bibcode:1993CPL...207..123L. doi:10.1016/0009-2614(93)87001-j. ISSN   0009-2614.
  2. Yin, Runsheng; Krabbenhoft, David; Bergquist, Bridget; Zheng, Wang; Lepak, Ryan; Hurley, James (2016). "Effects of mercury and thallium concentrations on high precision determination of mercury isotopic composition by Neptune Plus multiple collector inductively coupled plasma mass spectrometry". Journal of Analytical Atomic Spectrometry. 31 (10): 2060–2068. doi:10.1039/C6JA00107F.
  3. 1 2 3 4 5 6 Shayesteh, Alireza; Shanshan Yu; Peter F. Bernath (2005). "Gaseous HgH2, CdH2, and ZnH2". Chemistry: A European Journal. 11 (16): 4709–4712. doi:10.1002/chem.200500332. ISSN   0947-6539. PMID   15912545.
  4. 1 2 3 Wang, Xuefeng; Andrews, Lester (2005). "Mercury dihydride forms a covalent molecular solid". Physical Chemistry Chemical Physics. 7 (5): 750–9. Bibcode:2005PCCP....7..750W. doi:10.1039/b412373e. ISSN   1463-9076. PMID   19791358.
  5. Shayesteh, Alireza; Yu, Shanshan; Bernath, Peter F. (2005). "Infrared Emission Spectra and Equilibrium Structures of Gaseous HgH2and HgD2". The Journal of Physical Chemistry A. 109 (45): 10280–10286. Bibcode:2005JPCA..10910280S. CiteSeerX   10.1.1.507.4752 . doi:10.1021/jp0540205. ISSN   1089-5639. PMID   16833322.