Digermane

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Digermane
Digermane.svg
Digermane-3D-vdW.png
Names
IUPAC name
Digermane
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.159.079 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
  • InChI=1S/Ge2H6/c1-2/h1-2H3
    Key: MOFQWXUCFOZALF-UHFFFAOYSA-N
  • InChI=1/Ge2H6/c1-2/h1-2H3
    Key: MOFQWXUCFOZALF-UHFFFAOYAF
  • [GeH3][GeH3]
Properties
Ge2H6
Molar mass 151.328 g/mol
AppearanceColorless gas
Density 1.98 kg/m3 [1]
Melting point −109 °C (−164 °F; 164 K)
Boiling point 29 °C (84 °F; 302 K)
Insoluble
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg
Danger
H220, H302, H312, H315, H319, H330, H335
P210, P260, P261, P264, P270, P271, P280, P284, P301+P312, P302+P352, P304+P340, P305+P351+P338, P310, P312, P320, P321, P322, P330, P332+P313, P337+P313, P362, P363, P377, P381, P403, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Digermane is an inorganic compound with the chemical formula Ge2H6. One of the few hydrides of germanium, it is a colourless liquid. Its molecular geometry is similar to ethane. [2]

Contents

Synthesis

Digermane was first synthesized and examined in 1924 by Dennis, Corey, and Moore. Their method involves the hydrolysis of magnesium germanide using hydrochloric acid. [3] Many of the properties of digermane and trigermane were determined in the following decade using electron diffraction studies. [4] Further considerations of the compound involved examinations of various reactions such as pyrolysis and oxidation.

Digermane is produced together with germane by the reduction of germanium dioxide with sodium borohydride. Although the major product is germane, a quantifiable amount of digermane is produced in addition to traces of trigermane. [5] It also arises by the hydrolysis of magnesium-germanium alloys. [6]

Reactions

The reactions of digermane exhibit some differences between analogous compounds of the Group 14 elements carbon and silicon. However, there are still some similarities seen, especially in regards to pyrolysis reactions.

The oxidation of digermane takes place at lower temperatures than monogermane. The product of the reaction, germanium oxide, has been shown to act in turn as a catalyst of the reaction. This exemplifies a fundamental difference between germanium and the other Group 14 elements carbon and silicon (carbon dioxide and silicon dioxide do not exhibit the same catalytic properties). [7]

2Ge2H6 + 7O2 → 4GeO2 + 6H2O

In liquid ammonia, digermane undergoes disproportionation. Ammonia acts as a weakly basic catalyst. Products of the reaction are hydrogen, germane, and a solid polymeric germanium hydride. [8]

Pyrolysis of digermane is proposed to follow multiple steps:

Ge2H6 → 2GeH3
GeH3 + Ge2H6 → GeH4 + Ge2H5
Ge2H5 → GeH2 + GeH3
GeH2 → Ge + H2
2GeH2 → GeH4 + Ge
nGeH2 → (GeH2)n

This pyrolysis has been found to be more endothermic than the pyrolysis of disilane. This difference is attributed to the greater strength of the Ge-H bond vs the Si-H bond. As seen in the last reaction of the mechanism above, pyrolysis of digermane may induce polymerization of the GeH2 group, where GeH3 acts as a chain propagator and molecular hydrogen gas is released. [9] The dehydrogenation of digermane on gold leads to the formation of germanium nanowires. [10]

Digermane is a precursor to Ge2H5ECF3, where E is either sulfur or selenium. These trifluoromethylthio and trifluoromethylseleno derivatives possess a markedly higher thermal stability than digermane itself. [11]

Applications

Digermane has a limited number of applications; germane itself is the preferred volatile germanium hydride. Generally, digermane is primarily used a precursor to germanium for use in various applications. Digermane can be used to deposit Ge-containing semiconductors via chemical vapor deposition. [12]

Related Research Articles

Germanium Chemical element, symbol Ge and atomic number 32

Germanium is a chemical element with the symbol Ge and atomic number 32. It is a lustrous, hard-brittle, grayish-white metalloid in the carbon group, chemically similar to its group neighbors silicon and tin. Pure germanium is a semiconductor with an appearance similar to elemental silicon. Like silicon, germanium naturally reacts and forms complexes with oxygen in nature.

Organometallic chemistry Study of organic compounds containing metal(s)

Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.

Diborane Chemical compound

Diborane(6), generally known as diborane, is the chemical compound consisting of boron and hydrogen with the formula B2H6. It is a colorless, pyrophoric gas with a repulsively sweet odor. Synonyms include boroethane, boron hydride, and diboron hexahydride. Diborane is a key boron compound with a variety of applications. It has attracted wide attention for its electronic structure. Its derivatives are useful reagents.

A nitrile is any organic compound that has a −C≡N functional group. The prefix cyano- is used interchangeably with the term nitrile in industrial literature. Nitriles are found in many useful compounds, including methyl cyanoacrylate, used in super glue, and nitrile rubber, a nitrile-containing polymer used in latex-free laboratory and medical gloves. Nitrile rubber is also widely used as automotive and other seals since it is resistant to fuels and oils. Organic compounds containing multiple nitrile groups are known as cyanocarbons.

Germane Chemical compound

Germane is the chemical compound with the formula GeH4, and the germanium analogue of methane. It is the simplest germanium hydride and one of the most useful compounds of germanium. Like the related compounds silane and methane, germane is tetrahedral. It burns in air to produce GeO2 and water. Germane is a group 14 hydride.

Ammonia borane Chemical compound

Ammonia borane (also systematically named amminetrihydridoboron), also called borazane, is the chemical compound with the formula H3NBH3. The colourless or white solid is the simplest molecular boron-nitrogen-hydride compound. It has attracted attention as a source of hydrogen fuel, but is otherwise primarily of academic interest.

Germanium dioxide, also called germanium(IV) oxide, germania, and salt of germanium, is an inorganic compound with the chemical formula GeO2. It is the main commercial source of germanium. It also forms as a passivation layer on pure germanium in contact with atmospheric oxygen.

Organogermanium compound

Organogermanium compounds are organometallic compounds containing a carbon to germanium or hydrogen to germanium chemical bond. Organogermanium chemistry is the corresponding chemical science. Germanium shares group 14 in the periodic table with silicon, tin and lead, and not surprisingly the chemistry of organogermanium is in between that of organosilicon compounds and organotin compounds.

Plumbane Chemical compound

Plumbane, PbH4, 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.

Beryllium hydride 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. It is used in rocket fuels Unlike the ionically bonded hydrides of the heavier Group 2 elements, beryllium hydride is covalently bonded.

Silicon tetrabromide Chemical compound

Silicon tetrabromide is the inorganic compound with the formula SiBr4. This colorless liquid has a suffocating odor due to its tendency to hydrolyze with release of hydrogen bromide. The general properties of silicon tetrabromide closely resemble those of the more commonly used silicon tetrachloride.

An insertion reaction is a chemical reaction where one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:

Germanium(II) hydroxide, normally written as Ge(OH)2, is a poorly characterised compound, sometimes called hydrous germanium(II) oxide or germanous hydroxide. It was first reported by Winkler in 1886.

1-Tetralone Chemical compound

1-Tetralone is a bicyclic aromatic hydrocarbon and a ketone. In terms of its structure, it can also be regarded as benzo-fused cyclohexanone. It is a colorless oil with a faint odor. It is used as starting material for agricultural and pharmaceutical agents. The carbon skeleton of 1-tetralone is found in natural products such as Aristelegone A (4,7-dimethyl-6-methoxy-1-tetralone) from the family of Aristolochiaceae used in traditional Chinese medicine.

Tetramethyldiborane Chemical compound

Dimethylborane, (CH3)2BH is the simplest dialkylborane, consisting of a methyl group substituted for a hydrogen in borane. As for other boranes it normally exists in the form of a dimer called tetramethyldiborane or tetramethylbisborane or TMDB ((CH3)2BH)2. Other combinations of methylation occur on diborane, including monomethyldiborane, trimethyldiborane, 1,2-dimethylborane, 1,1-dimethylborane and trimethylborane. At room temperature the substance is at equilibrium between these forms. The methylboranes were first prepared by H. I. Schlesinger and A. O. Walker in the 1930s.

R. Tom Baker is an inorganic chemist known for the development and application of inorganic transition metal-based catalysis.

Germanium(II) hydrides, also called germylene hydrides, are a class of Group 14 compounds consisting of low-valent germanium and a terminal hydride. They are also typically stabilized by an electron donor-acceptor interaction between the germanium atom and a large, bulky ligand.

An oxyhydride is a mixed anion compound containing both oxide O2− and hydride ions H−. These compounds may be unexpected as the hydrogen and oxygen could be expected to react to form water. But if the metals making up the anions are electropositive enough, and the conditions are reducing enough, solid materials can be made that combine hydrogen and oxygen in the negative ion role.

Germyl, trihydridogermanate(1-), trihydrogermanide, trihydridogermyl or according to IUPAC Red Book: germanide is an anion containing germanium and hydrogen 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. Trihydridogermanate(1-) is the base for germane when it loses a proton.

Germanium tetrabromide Chemical compound

Germanium tetrabromide is an inorganic compound with the formula GeBr4. It can be formed by reacting solid germanium and gaseous bromine.

References

  1. ↑ Haynes, William M., ed. (2016). CRC Handbook of Chemistry and Physics (97th ed.). Boca Raton, FL: CRC Press. pp. 4–61. ISBN   9781498754293.
  2. ↑ Pauling, Linus; Laubengayer, A. W.; Hoard, J. L. (1938). "The Electron Diffraction Study of Digermane and Trigermane". Journal of the American Chemical Society. 60 (7): 1605–1607. doi:10.1021/ja01274a024.
  3. ↑ Dennis, L.M.; Corey, R. B.; Moore, R.W. (1924). "Germanium. VII. The Hydrides of Germanium". J. Am. Chem. Soc. 46 (3): 657–674. doi:10.1021/ja01668a015.
  4. ↑ Pauling, L.; Laubengayer, A.W.; Hoard, J.L. (1938). "The electron diffraction study of digermane and trigermane". J. Am. Chem. Soc. 60 (7): 1605–1607. doi:10.1021/ja01274a024.
  5. ↑ Jolly, William L.; Drake, John E. (1963). Hydrides of Germanium, Tin, Arsenic, and Antimony. Inorganic Syntheses. Vol. 7. pp. 34–44. doi:10.1002/9780470132388.ch10. ISBN   9780470132388.
  6. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  7. ↑ Emeleus, H.J.; Gardner, E.R. "The oxidation of monogermane and digermane". J. Chem. Soc. 1938: 1900–1909. doi:10.1039/jr9380001900.
  8. ↑ Dreyfuss, R.M.; Jolly, W.L. (1968). "Disproportionation of digermane in liquid ammonia". Inorganic Chemistry. 7 (12): 2645–2646. doi:10.1021/ic50070a037.
  9. ↑ Johnson, O.H. (1951). "The Germanes and their Organo Derivatives". Chem. Rev. 48 (2): 259–297. doi:10.1021/cr60150a003. PMID   24540662.
  10. ↑ Gamalski, A.D.; Tersoff, J.; Sharma, R.; Ducati, C.; Hofmann, S. (2010). "Formation of Metastable Liquid Catalyst during Subeutectic Growth of Germanium Nanowires". Nano Lett. 10 (8): 2972–2976. Bibcode:2010NanoL..10.2972G. doi:10.1021/nl101349e. PMID   20608714.
  11. ↑ Holmes-Smith, R.D.; Stobart, S.R. (1979). "Trifluoromethylthio and trifluoromethylseleno derivatives of germane and digermane". Inorg. Chem. 18 (3): 538–543. doi:10.1021/ic50193a002.
  12. ↑ Xie, J.; Chizmeshya, A.V.G.; Tolle, J.; D'Costa, V.R.; Menendez, J.; Kouventakis, J. (2010). "Synthesis, Stability Range, and Fundamental Properties of Si-Ge-Sn Semiconductors Grown Directly on Si(100) and Ge(100) Platforms". Chemistry of Materials. 22 (12): 3779–3789. doi:10.1021/cm100915q.
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