Lithium borohydride (LiBH₄) is a

borohydride Borohydride refers to the anion , which is also called tetrahydroborate, and its salts. Borohydride or hydroborate is also the term used for compounds containing , where ''n'' is an integer from 0 to 3, for example cyanoborohydride or cyanotrihyd ...

and known in

organic synthesis Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one o ...

as a

reducing agent In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are commonly reducing agents include the Earth meta ...

for

ester In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ar ...

s. Although less common than the related

sodium borohydride Sodium borohydride, also known as sodium tetrahydridoborate and sodium tetrahydroborate, is an inorganic compound with the formula Na BH4. This white solid, usually encountered as an aqueous basic solution, is a reducing agent that finds appli ...

, the lithium salt offers some advantages, being a stronger reducing agent and highly soluble in ethers, whilst remaining safer to handle than

lithium aluminium hydride Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula Li Al H4. It is a white solid, discovered by Finholt, Bond and Schlesinger in 1947. This compound is used as a reducing agent in organic ...

.Luca Banfi, Enrica Narisano, Renata Riva, Ellen W. Baxter, "Lithium Borohydride" e-EROS Encyclopedia of Reagents for Organic Synthesis, 2001, John Wiley & Sons. .

Preparation

Lithium borohydride may be prepared by the metathesis reaction, which occurs upon ball-milling the more commonly available

and

lithium bromide Lithium bromide (LiBr) is a chemical compound of lithium and bromine. Its extreme hygroscopic character makes LiBr useful as a desiccant in certain air conditioning systems.Wietelmann, Ulrich and Bauer, Richard J. (2005) "Lithium and Lithium Compo ...

: : NaBH₄ + LiBr → NaBr + LiBH₄ Alternatively, it may be synthesized by treating

boron trifluoride Boron trifluoride is the inorganic compound with the formula BF3. This pungent, colourless, and toxic gas forms white fumes in moist air. It is a useful Lewis acid and a versatile building block for other boron compounds. Structure and bondin ...

with

lithium hydride Lithium hydride is an inorganic compound with the formula Li H. 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 solub ...

diethyl ether Diethyl ether, or simply ether, is an organic compound in the ether class with the formula , sometimes abbreviated as (see Pseudoelement symbols). It is a colourless, highly volatile, sweet-smelling ("ethereal odour"), extremely flammable liq ...

: : BF₃ + 4 LiH → LiBH₄ + 3 LiF

Reactions

Lithium borohydride is a stronger reducing agent than

. In mixtures of

methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is a ...

and

, lithium borohydride is able to reduce esters to alcohols and

primary Primary or primaries may refer to: Arts, entertainment, and media Music Groups and labels * Primary (band), from Australia * Primary (musician), hip hop musician and record producer from South Korea * Primary Music, Israeli record label Works * ...

amide In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula , where R, R', and R″ represent organic groups or hydrogen atoms. The amide group is called a peptide bond when it is ...

s to

amine In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituen ...

s. In contrast, these substrates are unaffected by sodium borohydride. The enhanced reactivity is attributed to the polarization of the carbonyl substrate by complexation to the lithium cation.

Chemoselectivity

The use of lithium borohydride is particularly advantageous in some preparations due to its higher

chemoselectivity Chemoselectivity is the preferential outcome of a chemical reaction over a set of possible alternative reactions. In another definition, chemoselectivity refers to the selective reactivity of one functional group in the presence of others; often ...

relative to other popular reducing agents such as

. For instance, unlike lithium aluminium hydride, lithium borohydride reduces esters,

nitrile In organic chemistry, a nitrile is any organic compound that has a functional group. The prefix ''cyano-'' is used interchangeably with the term ''nitrile'' in industrial literature. Nitriles are found in many useful compounds, including met ...

lactones Lactones are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-one structure (), or analogues having unsaturation or heteroatoms replacing one or more carbon atoms of the ring. Lactones are formed by intramolecular esterification of the c ...

, primary amides, and

epoxide In organic chemistry, an epoxide is a cyclic ether () with a three-atom ring. This ring approximates an equilateral triangle, which makes it strained, and hence highly reactive, more so than other ethers. They are produced on a large scale for ...

s, while sparing

nitro group In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups (). The nitro group is one of the most common explosophores (functional group that makes a compound explosive) used globally. The nitr ...

carbamic acid Carbamic acid, which might also be called aminoformic acid or aminocarboxylic acid, is the chemical compound with the formula . It can be obtained by the reaction of ammonia and carbon dioxide at very low temperatures, which also yields an equ ...

alkyl halides The haloalkanes (also known as halogenoalkanes or alkyl halides) are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely us ...

, and

secondary Secondary may refer to: Science and nature * Secondary emission, of particles ** Secondary electrons, electrons generated as ionization products * The secondary winding, or the electrical or electronic circuit connected to the secondary winding i ...

tertiary Tertiary ( ) is a widely used but obsolete term for the geologic period from 66 million to 2.6 million years ago. The period began with the demise of the non-avian dinosaurs in the Cretaceous–Paleogene extinction event, at the start ...

amides.

Hydrogen generation

Lithium borohydride reacts with water to produce hydrogen. This reaction can be used for hydrogen generation.

Energy storage

Lithium borohydride is renowned as one of the highest- energy-density chemical

energy carrier An energy carrier is a substance (fuel) or sometimes a phenomenon (energy system) that contains energy that can be later converted to other forms such as mechanical work or heat or to operate chemical or physical processes. Such carriers includ ...

s. Although presently of no practical importance, the solid liberates 65 MJ/ kg heat upon treatment with atmospheric oxygen. Since it has a density of 0.67 g/cm³, oxidation of liquid lithium borohydride gives 43 MJ/L. In comparison, gasoline gives 44 MJ/kg (or 35 MJ/L), while liquid hydrogen gives 120 MJ/kg (or 8.0 MJ/L).The greater ratio of energy density to specific energy for hydrogen is because of the very low mass density (0.071 g/cm³). The high specific energy density of lithium borohydride has made it an attractive candidate to propose for automobile and rocket fuel, but despite the research and advocacy, it has not been used widely. As with all chemical-hydride-based energy carriers, lithium borohydride is very complex to recycle (i.e. recharge) and therefore suffers from a low

energy conversion efficiency Energy conversion efficiency (''η'') is the ratio between the useful output of an energy conversion machine and the input, in energy terms. The input, as well as the useful output may be chemical, electric power, mechanical work, light (radia ...

. While batteries such as

lithium-ion A lithium-ion or Li-ion battery is a type of rechargeable battery which uses the reversible reduction of lithium ions to store energy. It is the predominant battery type used in portable consumer electronics and electric vehicles. It also sees ...

carry an energy density of up to 0.72 MJ/kg and 2.0 MJ/L, their DC-to-DC conversion efficiency can be as high as 90%. In view of the complexity of recycling mechanisms for metal hydrides, (1977) lithium borohydride recycling from lithium borate via a methyl borate intermediate. such high energy-conversion efficiencies are not practical with present technology.

Notes

References

{{Lithium compounds Borohydrides Lithium salts Reducing agents el:Υδρίδιο του λιθίου