Lithium tetrahydridogallate

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Lithium tetrahydridogallate
Lithium gallium hydride.png
Names
IUPAC name
Lithium tetrahydridogallate(III)
Other names
Lithium gallium hydride
Lithium tetrahydrogallate
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/Ga.Li.4H/q-1;+1;;;;
    Key: FRRLJROQAGRKMM-UHFFFAOYSA-N
  • [Li+].[GaH4-]
Properties
LiGaH4
Molar mass 80.7 g/mol
Appearancewhite crystals (pure samples)
Melting point 70 °C (158 °F; 343 K) (decomposes)
Reacts
Related compounds
Related hydride
Gallium hydride
Sodium tetrahydridogallate
Potassium tetrahydridogallate
Cesium tetrahydridogallate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Lithium tetrahydridogallate is the inorganic compound with formula LiGaH4. It is a white solid similar to but less thermally robust than lithium aluminium hydride. [1]

Contents

Synthesis

Lithium tetrahydridogallate was first reported by Finholt, Bond and Schlesinger. [1] It is prepared by the reaction of lithium hydride and an ethereal solution of gallium trichloride: [2]

GaCl3 + 4 LiH → LiGaH4 + 3 LiCl

The reactants are combined at -80 °C and then allowed to get to room temperature. Higher yields (80-95%) and reaction rates are possible by using gallium tribromide.

Properties

Lithium tetrahydridogallate is easily dissolved in diethyl ether with which it forms a stable complex, making removal of the solvent difficult. Ethereal solutions of LiGaH4 are indefinitely stable if sealed in glass vessels at 0 °C. Lithium tetrahydridogallate can also be dissolved in tetrahydrofuran and diglyme. [3]

Lithium tetrahydridogallate slowly decomposes at room temperature. The decomposition is fast at 70 °C and the reaction produces lithium hydride, gaseous hydrogen and metallic gallium. [4] The reaction is autocatalyzed by the small particles of metallic gallium being formed.

Reactivity

It can be generally stated that lithium tetrahydridogallate's reactivity is similar to lithium tetrahydridoaluminate's reactivity, but the first is less stable. [5] This is due to the susceptibility of the gallium-hydrogen bonds to hydrolysis. As a consequence LiGaH4 is usually prepared in the absence of air. [6]

Lithium tetrahydridogallate violently reacts with water by releasing 4 moles of gaseous hydrogen. [7] It can generally be stated that lithium gallium hydride reacts with protic solvents. [6]

Ethereal solutions of LiGaH4 are strongly reductant but less than LiBH4 and LiAlH4. It reacts with primary and secondary amines to release gaseous hydrogen. LiGaH4 reduces acetamide and acetonitrile to ethylamine. Aliphatic acids, aldehydes and ketones are reduced to the corresponding alcohols. Aromatic nitriles, aldehydes, ketones and esters are not reduced. [7]

Usage

Lithium gallium hydride is often used to prepare other complex gallium hydrides. For example, it can be used to convert thallium trichloride into thallium tetrahydrogallate (which appears as a white solid powder that decomposes above -90 °C) and silver perchlorate into silver tetrahydrogallate (which appears as an orange-reddish solid powder that rapidly decomposes in ethereal solution above -75 °C). In the first case the reaction is carried out at a temperature of -115 °C, in the latter the reaction is carried out at -100 °C. [6]

Reacting lithium gallium hydride and sodium hydride or potassium hydride yields respectively the more stable sodium tetrahydrogallate (decomposes in argon atmosphere at 165 °C) and potassium tetrahydrogallate (decomposes at about 230 °C). Both appear as white crystalline powders e can be preserved in the absence of water and moisture for more than one year. [7]

Digallane is produced by reaction between lithium tetrahydrogallate and monochlorogallane. [8]

Related Research Articles

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

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

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

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<span class="mw-page-title-main">Indium(III) chloride</span> Chemical compound

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

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

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<span class="mw-page-title-main">Carbonyl reduction</span> Organic reduction of any carbonyl group by a reducing agent

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

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3
. It is a photosensitive, colourless gas that cannot be concentrated in pure form. Gallane is both the simplest member of the gallanes, and the prototype of the monogallanes. It has no economic uses, and is only intentionally produced for academic reasons.

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

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<span class="mw-page-title-main">Aluminium compounds</span>

Aluminium (or aluminum) combines characteristics of pre- and post-transition metals. Since it has few available electrons for metallic bonding, like its heavier group 13 congeners, it has the characteristic physical properties of a post-transition metal, with longer-than-expected interatomic distances. Furthermore, as Al3+ is a small and highly charged cation, it is strongly polarizing and aluminium compounds tend towards covalency; this behaviour is similar to that of beryllium (Be2+), an example of a diagonal relationship. However, unlike all other post-transition metals, the underlying core under aluminium's valence shell is that of the preceding noble gas, whereas for gallium and indium it is that of the preceding noble gas plus a filled d-subshell, and for thallium and nihonium it is that of the preceding noble gas plus filled d- and f-subshells. Hence, aluminium does not suffer the effects of incomplete shielding of valence electrons by inner electrons from the nucleus that its heavier congeners do. Aluminium's electropositive behavior, high affinity for oxygen, and highly negative standard electrode potential are all more similar to those of scandium, yttrium, lanthanum, and actinium, which have ds2 configurations of three valence electrons outside a noble gas core: aluminium is the most electropositive metal in its group. Aluminium also bears minor similarities to the metalloid boron in the same group; AlX3 compounds are valence isoelectronic to BX3 compounds (they have the same valence electronic structure), and both behave as Lewis acids and readily form adducts. Additionally, one of the main motifs of boron chemistry is regular icosahedral structures, and aluminium forms an important part of many icosahedral quasicrystal alloys, including the Al–Zn–Mg class.

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

Nitrogen pentahydride, also known as ammonium hydride is a hypothetical compound with the chemical formula NH5. There are two theoretical structures of nitrogen pentahydride. One structure is trigonal bipyramidal molecular geometry type NH5 molecule. Its nitrogen atom and hydrogen atoms are covalently bounded, and its symmetry group is D3h. Another predicted structure of nitrogen pentahydride is an ionic compound, make up of an ammonium ion and a hydride ion (NH4+H). Until now, no one has synthesized this substance, or proved its existence, and related experiments have not directly observed nitrogen pentahydride. It is only speculated that it may be a reactive intermediate based on reaction products. Theoretical calculations show this molecule is thermodynamically unstable. The reason might be similar to the instability of nitrogen pentafluoride, so the possibility of its existence is low. However, nitrogen pentahydride might exist in special conditions or high pressure. Nitrogen pentahydride was considered for use as a solid rocket fuel for research in 1966.

Gallium compounds are compounds containing the element gallium. These compounds are found primarily in the +3 oxidation state. The +1 oxidation state is also found in some compounds, although it is less common than it is for gallium's heavier congeners indium and thallium. For example, the very stable GaCl2 contains both gallium(I) and gallium(III) and can be formulated as GaIGaIIICl4; in contrast, the monochloride is unstable above 0 °C, disproportionating into elemental gallium and gallium(III) chloride. Compounds containing Ga–Ga bonds are true gallium(II) compounds, such as GaS (which can be formulated as Ga24+(S2−)2) and the dioxan complex Ga2Cl4(C4H8O2)2. There are also compounds of gallium with negative oxidation states, ranging from -5 to -1, most of these compounds being magnesium gallides (MgxGay).

References

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  3. T. N. Dymova; Yu. M. Dergachev (December 1973). "Solubility of rubidium tetrahydrogallate in diglyme". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 22 (12): 2597–2599. doi:10.1007/BF00926118.
  4. P. Claudy; J. Bouix (1970). "Étude de la préparation et de la décomposition thermique du gallanate de lithium". Bulletin de la Société Chimique de France: 1302.
  5. M. J. Pitt; L. A. Battle (2016). P. G. Urben (ed.). Bretherick's Handbook of Reactive Chemical Hazards. Vol. 1 (5 ed.). Oxford: Elsevier. p. 1452.
  6. 1 2 3 Booth, Harold Simmons (1939). Inorganic syntheses. McGraw-Hill. pp. 45–47. ISBN   978-0-07-048517-4.
  7. 1 2 3 Emeléus, H. J.; Ebsworth, E. A. V.; Maddock, A. G. (2011). New pathways in inorganic chemistry. Cambridge University Press. ISBN   978-0-521-27913-0.
  8. Souter, Philip F.; Andrews, Lester; Downs, Anthony J. (December 1994). "Observed and calculated Raman spectra of the Ga2H6 and Ga2D6 molecules". The Journal of Physical Chemistry. 98 (49): 12824–12827. doi:10.1021/j100100a004.