Lithium aluminium hydride

Lithium aluminium hydride

Names
Preferred IUPAC name Lithium tetrahydridoaluminate(III)
Systematic IUPAC name Lithium alumanuide
Other names Lithium aluminium hydride Lithal Lithium alanate Lithium aluminohydride Lithium tetrahydridoaluminate Lithium tetrahydridoaluminate(III)
Identifiers
CAS Number	16853-85-3 Y 14128-54-2 (2H4) Y
Abbreviations	LAH
ChEBI	CHEBI:30142 Y
ChemSpider	26150 Y
EC Number	240-877-9
Gmelin Reference	13167
Jmol 3D model	Interactive image
PubChem	28112 11062293 (2H4) 11094533 (3H4)
RTECS number	BD0100000
InChI InChI=1S/Al.Li.4H/q-1;+1;;;; Y Key: OCZDCIYGECBNKL-UHFFFAOYSA-N Y InChI=1S/Al.Li.4H/q-1;+1;;;; Key: OCZDCIYGECBNKL-UHFFFAOYSA-N
SMILES [Li+].[AlH4-]
Properties
Chemical 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
Solubility in diethyl ether	39.5 g/100 mL
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 (ΔfG˚)	-48.4 kJ/mol
Vapor pressure	{{{value}}}
Related compounds
Related hydride	aluminium hydride sodium borohydride sodium hydride Sodium aluminium hydride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references

Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula LiAlH₄. It was 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.

Properties, structure, preparation

SEM image of LAH powder

LAH is a white solid, but commercial samples are usually gray due to contamination. 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. Some commercial materials contain mineral oil to inhibit reactions with atmospheric moisture, but more commonly it is packed in moisture-proof plastic sacks.

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

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.

Structure

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.

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

Preparation

LiAH was first prepared from the reaction between lithium hydride (LiH) and aluminium chloride:

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:

Na + Al + 2 H₂ → NaAlH₄

LiAH 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 LiAH, with subsequent precipitation of LiAH to yield a product containing around 1% w/w LiCl.

Solubility data

Solubility of LiAlH₄ (mol/L)

	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.

Thermodynamic data

The table summarizes thermodynamic data for LAH and reactions involving LAH, 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

LAH is metastable at room temperature. During prolonged storage it slowly decomposes to Li₃AlH₆ and LiH. 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:

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, immediately followed by decomposition into solid Li₃AlH₆, although R1 is known to proceed below the melting point of LiAlH₄ as well. At about 200 °C, Li₃AlH₆ decomposes into LiH (R2) and Al which subsequently convert into LiAl above 400 °C (R3). 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.

Applications

Use in organic chemistry

Lithium aluminium hydride is widely used in organic chemistry as a reducing agent. It is more powerful than the related reagent sodium borohydride owing to the weaker Al-H bond compared to the B-H bond. 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, nitro, nitrile, imine, oxime, 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.

LAH is most commonly used for the reduction of esters and carboxylic acids 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 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. 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.

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.

Lithium aluminium hydride also reduces alkyl halides to alkanes, . 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.

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

Inorganic chemistry

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:

LiAlH₄ + 4 NaCl → 4 NaH + LiCl + AlCl₃

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

LiAlH₄ + 4NH₃ → Li[Al(NH₂)₄] + 4H₂

Hydrogen storage

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, 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. 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. 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

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:

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:

NaAlH₄ + LiCl → LiAlH₄ + NaCl

KAlH₄ + LiCl → LiAlH₄ + KCl

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

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:

See also

• Hydride
• Sodium borohydride
• Sodium hydride