Lithium aluminium hydride

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Lithium aluminium hydride
Wireframe model of lithium aluminium hydride Unit cell ball and stick model of lithium aluminium hydride
100 grams of lithium aluminium hydride
Identifiers
Abbreviations LAH
CAS number 16853-85-3 YesY, 14128-54-2 (2H4)
PubChem 28112 YesY, 11062293 (2H4YesY, 11094533 (3H4YesY
ChemSpider 26150 YesY
EC number 240-877-9
ChEBI CHEBI:30142 YesY
RTECS number BD0100000
Gmelin Reference 13167
Jmol-3D images Image 1
Properties
Molecular formula LiAlH4
Molar mass 37.95 g/mol
Appearance white crystals (pure samples)
grey powder (commercial material)
hygroscopic
Odor odorless
Density 0.917 g/cm3, solid
Melting point 150 °C (302 °F; 423 K) (decomposes)
Solubility in water Reacts
Solubility in tetrahydrofuran 112.332 g L−1
Structure
Crystal structure monoclinic
Space group P21/c
Thermochemistry
Specific
heat capacity
C
86.4 J/mol K
Std molar
entropy
So298
87.9 J/mol K
Std enthalpy of
formation
ΔfHo298
-117 kJ/mol
Gibbs free energy ΔG -48.4 kJ/mol
Hazards[1]
GHS pictograms Water-react. 1
GHS signal word DANGER
GHS hazard statements H260
EU Index 001-002-00-4
R/S statement R15, S7/8, S24/25, S43
Main hazards highly flammable
NFPA 704
Flammability code 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g., diesel fuel Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorus Special hazard W: Reacts with water in an unusual or dangerous manner. E.g., cesium, sodiumNFPA 704 four-colored diamond
Flash point 125 °C (257 °F; 398 K)
Related compounds
Related hydride aluminium hydride
sodium borohydride
sodium hydride
Sodium aluminium hydride
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 YesY (verify) (what is: YesY/N?)
Infobox references

Lithium aluminium hydride, commonly abbreviated to LAH or known as LithAl, is an inorganic compound with the chemical formula LiAlH4. It was discovered by Finholt, Bond and Schlesinger in 1947.[2] 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.

Properties, structure, preparation[edit]

SEM image of LAH powder

LAH is a white solid, but commercial samples are usually gray due to contamination.[3] This material can be purified by recrystallization from diethyl ether. Large-scale purifications employ a Soxhlet extractor. Commonly, the impure gray material is used in synthesis, since the impurities are innocuous and can be easily separated from the organic products. The pure powdered material is pyrophoric, but not its large crystals.[4] Some commercial materials contain mineral oil to inhibit reactions with atmospheric moisture, but more commonly it is packed in moisture-proof plastic sacks.[5]

LAH violently reacts with water, including atmospheric moisture. The reaction proceeds according to the following idealized equation:[3]

LiAlH4 + 4 H2O → LiOH + Al(OH)3 + 4 H2

This reaction provides a useful method to generate hydrogen in the laboratory. Aged, air-exposed samples often appear white because they have absorbed enough moisture to generate a mixture of the white compounds lithium hydroxide and aluminium hydroxide.[6]

Structure[edit]

The crystal structure of LAH; Li atoms are purple and AlH4 tetrahedra are tan.

LAH crystallizes in the monoclinic space group P21/c. The unit cell has the dimensions: a = 4.82, b = 7.81, and c = 7.92 Å, α = γ=90° and β=112°. In the structure, Li+ centers are surrounded by five AlH
4
tetrahedra. The Li+ centers are bonded to one hydrogen atom from each of the surrounding tetrahedra creating a bipyramid arrangement. At high pressures (>2.2 GPa) a phase transition may occur to give β-LAH.[7]

X-ray powder diffraction pattern of as-received LiAlH4. The asterisk designates an impurity, possibly LiCl.

Preparation[edit]

LAH was first prepared from the reaction between lithium hydride (LiH) and aluminium chloride:[2][3]

4 LiH + AlCl3 → LiAlH4 + 3 LiCl

In addition to this method, the industrial synthesis entails the initial preparation of sodium aluminium hydride from the elements under high pressure and temperature:[8]

Na + Al + 2 H2 → NaAlH4

LAH is then prepared by a salt metathesis reaction according to:

NaAlH4 + LiCl → LiAlH4 + NaCl

which proceeds in a high yield of LAH. LiCl is removed by filtration from an ethereal solution of LAH, with subsequent precipitation of LAH to yield a product containing around 1% w/w LiCl.[8]

Solubility data[edit]

Solubility of LiAlH4 (mol/L)[9]
Temperature (°C)
Solvent 0 25 50 75 100
Diethyl ether 5.92
THF 2.96
Monoglyme 1.29 1.80 2.57 3.09 3.34
Diglyme 0.26 1.29 1.54 2.06 2.06
Triglyme 0.56 0.77 1.29 1.80 2.06
Tetraglyme 0.77 1.54 2.06 2.06 1.54
Dioxane 0.03
Dibutyl ether 0.56

LAH is soluble in many ethereal solutions. However, it may spontaneously decompose due to the presence of catalytic impurities, though, it appears to be more stable in tetrahydrofuran (THF). Thus, THF is preferred over, e.g., diethyl ether, despite the lower solubility.[9]

Thermodynamic data[edit]

The table summarizes thermodynamic data for LAH and reactions involving LAH,[10][11] in the form of standard enthalpy, entropy, and Gibbs free energy change, respectively.

Thermodynamic data for reactions involving LiAlH4
Reaction ΔH°
(kJ/mol)
ΔS°
(J/(mol·K))
ΔG°
(kJ/mol)
Comment
Li (s) + Al (s) + 2 H2(g) → LiAlH4 (s) −116.3 −240.1 −44.7 Standard formation from the elements.
LiH (s) + Al (s) + 3/2 H2 (g) → LiAlH4 (s) −95.6 −180.2 237.6 Using ΔH°f(LiH) = −90.579865, ΔS°f(LiH) = −679.9, and ΔG°f(LiH) = −67.31235744.
LiAlH4 (s) → LiAlH4 (l) 22 Heat of fusion. Value might be unreliable.
LiAlH4 (l) → ⅓ Li3AlH6 (s) + ⅔ Al (s) + H2 (g) 3.46 104.5 −27.68 ΔS° calculated from reported values of ΔH° and ΔG°.

Thermal decomposition[edit]

LAH is metastable at room temperature. During prolonged storage it slowly decomposes to Li3AlH6 and LiH.[12] This process can be accelerated by the presence of catalytic elements, such as titanium, iron or vanadium.

Differential scanning calorimetry of as-received LiAlH4.

When heated LAH decomposes in a three-step reaction mechanism:[12][13][14]

3 LiAlH4 → Li3AlH6 + 2 Al + 3 H2 (R1)
2 Li3AlH6 → 6 LiH + 2 Al + 3 H2 (R2)
2 LiH + 2 Al → 2 LiAl + H2 (R3)

R1 is usually initiated by the melting of LAH in the temperature range 150–170 °C,[15][16][17] immediately followed by decomposition into solid Li3AlH6, although R1 is known to proceed below the melting point of LiAlH4 as well.[18] At about 200 °C, Li3AlH6 decomposes into LiH (R2)[12][14][17] and Al which subsequently convert into LiAl above 400 °C (R3).[14] Reaction R1 is effectively irreversible. R3 is reversible with an equilibrium pressure of about 0.25 bar at 500 °C. R1 and R2 can occur at room temperature with suitable catalysts.[19]

Applications[edit]

Use in organic chemistry[edit]

Lithium aluminium hydride is widely used in organic chemistry as a reducing agent.[3] It is more powerful than the related reagent sodium borohydride owing to the weaker Al-H bond compared to the B-H bond.[20] Often as a solution in diethyl ether and followed by an acid workup, it will convert esters, carboxylic acids, acyl chlorides, aldehydes, and ketones into the corresponding alcohols (see: carbonyl reduction). Similarly, it converts amide,[21][22] nitro, nitrile, imine, oxime,[23] and azide compounds into the amines (see: amide reduction). It reduces quaternary ammonium cations into the corresponding tertiary amines. Reactivity can be tuned by replacing hydride groups by alkoxy groups. Despite handling problems associated with its reactivity, it is used even at the small-industrial scale, although for large-scale reductions the related reagent sodium bis(2-methoxyethoxy)aluminium hydride is more commonly used.[24]

LAH is most commonly used for the reduction of esters[25][26] and carboxylic acids[27] to primary alcohols; prior to the advent of LiAlH4 this was a difficult conversion involving sodium metal in boiling ethanol (the Bouveault-Blanc reduction). Aldehydes and ketones[28] can also be reduced to alcohols by LAH, but this is usually done using milder reagents such as NaBH4; α,β-unsaturated ketones are reduced to allylic alcohols.[29] When epoxides are reduced using LAH, the reagent attacks the less hindered end of the epoxide, usually producing a secondary or tertiary alcohol. Epoxycyclohexanes are reduced to give axial alcohols preferentially.[30]

Partial reduction of acid chlorides to give the corresponding aldehyde product cannot proceed via LAH, since the latter reduces all the way to the primary alcohol. Instead, the milder lithium aluminium tri(t-butoxy)hydride, which reacts significantly faster with the acid chloride than with the aldehyde, must be used. For example, when isovaleric acid is treated with thionyl chloride to give isovaleroyl chloride, it can then be reduced via lithium aluminium tri(t-butoxy)hydride to give isovaleraldehyde in 65% yield.[31]

Alcohol Epoxide alcohol2 alcohol3 alcohol4 Aldehyde Nitrile Amide amine1 Carboxylic acid alcohol5 azide amine2 Ester KetoneLAH rxns.png

Lithium aluminium hydride also reduces alkyl halides to alkanes, .[32][33] Alkyl iodides react the fastest, followed by alkyl bromides and then alkyl chlorides. Primary halides are the most reactive followed by secondary halides. Tertiary halides react only in certain cases.[34]

Lithium aluminium hydride does not reduce simple alkenes or arenes. Alkynes are reduced only if an alcohol group is nearby.[35]

Inorganic chemistry[edit]

LAH is widely used to prepare main group and transition metal hydrides from the corresponding metal halides. For example, sodium hydride (NaH) can be prepared from sodium chloride (NaCl) through the following reaction:[10]

LiAlH4 + 4 NaCl → 4 NaH + LiCl + AlCl3

LAH also reacts with many inorganic ligands to form coordinated alumina complexes associated with lithium ions.[10]

LiAlH4 + 4NH3 → Li[Al(NH2)4] + 4H2

Hydrogen storage[edit]

Volumetric and gravimetric hydrogen storage densities of different hydrogen storage methods. Metal hydrides are represented with squares and complex hydrides with triangles (including LiAlH4). Reported values for hydrides are excluding tank weight. DOE FreedomCAR targets are including tank weight.

LiAlH4 contains 10.6 wt% hydrogen, thereby making LAH a potential hydrogen storage medium for future fuel cell-powered vehicles. The high hydrogen content, as well as the discovery of reversible hydrogen storage in Ti-doped NaAlH4,[36] have sparked renewed research into LiAlH4 during the last decade. A substantial research effort has been devoted to accelerating the decomposition kinetics by catalytic doping and by ball milling.[37] In order to take advantage of the total hydrogen capacity, the intermediate compound LiH must be dehydrogenated as well. Due to its high thermodynamic stability this requires temperatures in excess of 400°C, which is not considered feasible for transportation purposes. Accepting LiH + Al as the final product, the hydrogen storage capacity is reduced to 7.96 wt%. Another problem related to hydrogen storage is the recycling back to LiAlH4 which, owing to its relatively low stability, requires an extremely high hydrogen pressure in excess of 10000 bar.[37] Cycling only reaction R2 — that is, using Li3AlH6 as starting material — would store 5.6 wt% hydrogen in a single step (vs. two steps for NaAlH4 which stores about the same amount of hydrogen). However, attempts at this process have not been successful so far.

Other tetrahydridoaluminiumates[edit]

A variety of salts analogous to LAH are known. NaH can be used to efficiently produce sodium aluminium hydride (NaAlH4) by metathesis in THF:

LiAlH4 + NaH → NaAlH4 + LiH

Potassium aluminium hydride (KAlH4) can be produced similarly in diglyme as a solvent:[38]

LiAlH4 + KH → KAlH4 + LiH

The reverse, i.e., production of LAH from either sodium aluminium hydride or potassium aluminium hydride can be achieved by reaction with LiCl or lithium hydride in diethyl ether or THF:[38]

NaAlH4 + LiCl → LiAlH4 + NaCl
KAlH4 + LiCl → LiAlH4 + KCl

"Magnesium alanate" (Mg(AlH4)2) arises similarly using MgBr2:[39]

2 LiAlH4 + MgBr2 → Mg(AlH4)2 + 2 LiBr

Red-Al (or SMEAH, NaAlH2(OC2H4OCH3)2) is synthesized by reacting sodium aluminum tetrahydride (NaAlH4) and 2-methoxyethanol:[40]

See also[edit]

References[edit]

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Further reading[edit]

External links[edit]