Beryllium hydride

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Beryllium hydride
Beryllium-hydride-3D-balls.png
Names
Other names
Beryllium dihydride
Beryllium hydride
Beryllane
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
UNII
  • InChI=1S/Be.2H Yes check.svgY
    Key: RWASOQSEFLDYLC-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Be.2H/rBeH2/h1H2
    Key: RWASOQSEFLDYLC-JICJMJRQAQ
  • [BeH2]
Properties
BeH2
Molar mass 11.03 g mol−1
Appearancewhite solid [1]
Density 0.65 g/cm3
Melting point 250 °C (482 °F; 523 K) decomposes
decomposes
Solubility insoluble in diethyl ether, toluene
Thermochemistry
30.124 J/mol K
Hazards
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 0.002 mg/m3
C 0.005 mg/m3 (30 minutes), with a maximum peak of 0.025 mg/m3 (as Be) [2]
REL (Recommended)
Ca C 0.0005 mg/m3 (as Be) [2]
IDLH (Immediate danger)
Ca [4 mg/m3 (as Be)] [2]
Related compounds
Other cations
lithium hydride, calcium hydride, boron hydrides
Related compounds
beryllium fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Beryllium hydride (systematically named poly[beryllane(2)] and beryllium dihydride) is an inorganic compound with the chemical formula (BeH
2
)n (also written ([BeH
2
]
)n or BeH
2
). 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 [1] (three-center two-electron bond).

Contents

Synthesis

Unlike the other group 2 metals, beryllium does not react with hydrogen. [3] Instead, BeH2 is prepared from preformed beryllium(II) compounds. It was first synthesised in 1951 by treating dimethylberyllium, Be(CH3)2, with lithium aluminium hydride, LiAlH4. [4]

Purer BeH2 forms from the pyrolysis of di-tert-butylberyllium, Be(C(CH3)3)2 at 210 °C. [5]

A route to highly pure samples involves the reaction of triphenylphosphine, PPh3, with beryllium borohydride, Be(BH4)2: [1]

Be(BH4)2 + 2 PPh3 → BeH2 + 2 Ph3PBH3

Structure

Gaseous form

Structure of gaseous BeH2. Beryllium-hydride-molecule-IR-3D-balls.png
Structure of gaseous BeH2.

Isolated molecules of BeH
2
(sometimes called dihydridoberyllium and written [BeH
2
]
to emphasize the differences with the solid state) are only stable as a dilute gas. When condensed, unsolvated BeH
2
will spontaneously autopolymerise.

Free molecular BeH2 produced by high-temperature electrical discharge has been confirmed to have linear geometry with a Be-H bond length of 133.376 pm. Its hybridisation is sp. [6]

Condensed Beryllium hydride

Subunit of structure of BeH2. Each Be is tetrahedral and each H is doubly bridging. BeH2 structure.svg
Subunit of structure of BeH2. Each Be is tetrahedral and each H is doubly bridging.

BeH2 is usually formed as an amorphous white solid, but a hexagonal crystalline form with a higher density (~0.78 g cm−3) was reported, [8] prepared by heating amorphous BeH2 under pressure, with 0.5-2.5% LiH as a catalyst.

A more recent investigation found that crystalline beryllium hydride has a body-centred orthorhombic unit cell, containing a network of corner-sharing BeH4 tetrahedra, in contrast to the flat, hydrogen-bridged, infinite chains previously thought to exist in crystalline BeH2. [7]

Studies of the amorphous form also find that it consists of a network of corner shared tetrahedra. [9]

Chemical properties

Reaction with water and acids

Beryllium hydride reacts slowly with water but is rapidly hydrolysed by acid such as hydrogen chloride to form beryllium chloride. [3]

BeH2 + 2 H2O → Be(OH)2 + 2 H2
BeH2 + 2 HCl → BeCl2 + 2 H2

Reaction with Lewis bases

The two-coordinate hydridoberyllium group can accept an electron-pair donating ligand (L) into the molecule by adduction: [10]

[BeH
2
]
+ L → [BeH
2
L]

Because these reactions are energetically favored, beryllium hydride has Lewis-acidic character.

The reaction with lithium hydride (in which the hydride ion is the Lewis base), forms sequentially LiBeH3 and Li2BeH4. [3] The latter contains the tetrahydridoberyllate(2-) anion BeH2−
4
.

Beryllium hydride reacts with trimethylamine, N(CH3)3 to form a dimeric adduct with bridging hydrides. [11] However, with dimethylamine, HN(CH3)2 it forms a trimeric beryllium diamide, [Be(N(CH3)2)2]3, and hydrogen. [3]

Related Research Articles

Cyclopentadiene is an organic compound with the formula C5H6. It is often abbreviated CpH because the cyclopentadienyl anion is abbreviated Cp.

In chemistry, a hydride is formally the anion of hydrogen (H). The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently 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">Diborane</span> Chemical compound

Diborane(6), generally known as diborane, is the chemical compound with the formula B2H6. It is a toxic, colorless, and pyrophoric gas with a repulsively sweet odor. Diborane is a key boron compound with a variety of applications. It has attracted wide attention for its electronic structure. Several of its derivatives are useful reagents.

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

Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula Li[AlH4] or LiAlH4. It is a white solid, discovered by Finholt, Bond and Schlesinger in 1947. This compound is used as a reducing agent in organic synthesis, especially for the reduction of esters, carboxylic acids, and amides. The solid is dangerously reactive toward water, releasing gaseous hydrogen (H2). Some related derivatives have been discussed for hydrogen storage.

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

Stibine (IUPAC name: stibane) is a chemical compound with the formula SbH3. A pnictogen hydride, this colourless, highly toxic gas is the principal covalent hydride of antimony, and a heavy analogue of ammonia. The molecule is pyramidal with H–Sb–H angles of 91.7° and Sb–H distances of 170.7 pm (1.707 Å). This gas has an offensive smell like hydrogen sulfide (rotten eggs).

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

Lithium hydride is an inorganic compound with the formula LiH. This alkali metal hydride is a colorless solid, although commercial samples are grey. Characteristic of a salt-like (ionic) hydride, it has a high melting point, and it is not soluble but reactive with all protic organic solvents. It is soluble and nonreactive with certain molten salts such as lithium fluoride, lithium borohydride, and sodium hydride. With a molar mass of 7.95 g/mol, it is the lightest ionic compound.

<span class="mw-page-title-main">Germane</span> 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.

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

Aluminium hydride (also known as alane and alumane) is an inorganic compound with the formula AlH3. Alane and its derivatives are common reducing (hydride addition) reagents in organic synthesis that are used in solution at both laboratory and industrial scales. In solution—typically in etherial solvents such tetrahydrofuran or diethyl ether—aluminium hydride forms complexes with Lewis bases, and reacts selectively with particular organic functional groups (e.g., with carboxylic acids and esters over organic halides and nitro groups), and although it is not a reagent of choice, it can react with carbon-carbon multiple bonds (i.e., through hydroalumination). 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.

Organophosphines are organophosphorus compounds with the formula PRnH3−n, where R is an organic substituent. These compounds can be classified according to the value of n: primary phosphines (n = 1), secondary phosphines (n = 2), tertiary phosphines (n = 3). All adopt pyramidal structures. Organophosphines are generally colorless, lipophilic liquids or solids. The parent of the organophosphines is phosphine (PH3).

<span class="mw-page-title-main">Group 2 organometallic chemistry</span>

Group 2 organometallic chemistry refers to the chemistry of compounds containing carbon bonded to any group 2 element. By far the most common group 2 organometallic compounds are the magnesium-containing Grignard reagents which are widely used in organic chemistry. Other organmetallic group 2 compounds are rare and are typically limited to academic interests.

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).

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, however ZnH2 itself has no common applications.

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

Pentacarbonylhydridomanganese is an organometallic compound with formula HMn(CO)5. This compound is one of the most stable "first-row" transition metal hydrides.

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.

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

Beryllium borohydride is an inorganic compound with the chemical formula Be(BH4)2.

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

Copper hydride is inorganic compound with the chemical formula CuHn where n ~ 0.95. It is a red solid, rarely isolated as a pure composition, that decomposes to the elements. Copper hydride is mainly produced as a reducing agent in organic synthesis and as a precursor to various catalysts.

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">Lithium tetrahydridogallate</span> Chemical compound

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

The inorganic imides are compounds containing an ion composed of nitrogen bonded to hydrogen with formula HN2−. Organic imides have the NH group, and two single or one double covalent bond to other atoms. The imides are related to the inorganic amides (H2N), the nitrides (N3−) and the nitridohydrides (N3−•H).

References

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  2. 1 2 3 NIOSH Pocket Guide to Chemical Hazards. "#0054". National Institute for Occupational Safety and Health (NIOSH).
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  5. G. E. Coates & F. Glockling (1954). "Di-tert.-butylberyllium and beryllium hydride". Journal of the Chemical Society : 2526–2529. doi:10.1039/JR9540002526.
  6. Peter F. Bernath; Alireza Shayesteh; Keith Tereszchuk; Reginald Colin (2002). "The Vibration-Rotation Emission Spectrum of Free BeH2". Science. 297 (5585): 1323–1324. Bibcode:2002Sci...297.1323B. doi:10.1126/science.1074580. PMID   12193780. S2CID   40961746.
  7. 1 2 Gordon S. Smith; Quintin C. Johnson; Deane K. Smith; D. E. Cox; Robert L. Snyder; Rong-Sheng Zhou & Allan Zalkin (1988). "The crystal and molecular structure of beryllium hydride". Solid State Communications . 67 (5): 491–494. Bibcode:1988SSCom..67..491S. doi:10.1016/0038-1098(84)90168-6.
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  9. Sujatha Sampath; Kristina M. Lantzky; Chris J. Benmore; Jörg Neuefeind & Joan E. Siewenie (2003). "Structural quantum isotope effects in amorphous beryllium hydride". J. Chem. Phys. 119 (23): 12499. Bibcode:2003JChPh.11912499S. doi:10.1063/1.1626638.
  10. Sharp, Stephanie B.; Gellene, Gregory I. (23 November 2000). "σ Bond Activation by Cooperative Interaction with ns2 Atoms: Be + nH
    2
    , n = 1−3". The Journal of Physical Chemistry A. 104 (46): 10951–10957. doi:10.1021/jp002313m.
  11. Shepherd Jr., Lawrence H.; Ter Haar, G. L.; Marlett, Everett M. (April 1969). "Amine complexes of beryllium hydride". Inorganic Chemistry. 8 (4): 976–979. doi:10.1021/ic50074a051.