Borazine

Last updated
Borazine
Borazine-dimensions-2D.svg
Borazine-elpot-3D-vdW.png
Borazine-3D-vdW.png
Names
Preferred IUPAC name
1,3,5,2,4,6-Triazatriborinane (only preselected [1] )
Other names
Cyclotriborazaneborazol
Inorganic benzene
Borazole
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.169.303 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/B3H6N3/c1-4-2-6-3-5-1/h1-6H Yes check.svgY
    Key: BGECDVWSWDRFSP-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/B3H6N3/c1-4-2-6-3-5-1/h1-6H
    Key: BGECDVWSWDRFSP-UHFFFAOYAU
  • [BH-]1-[NH+]=[BH-]-[NH+]=[BH-]-[NH+]=1
Properties
B3H6N3
Molar mass 80.50 g/mol
AppearanceColorless liquid
Density 0.81 g/cm3
Melting point −58 °C (−72 °F; 215 K)
Boiling point 53 °C (127 °F; 326 K) (55 °C at 105 Pa)
-49.6·10−6 cm3/mol
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 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 fuelInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
2
1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Borazine, also known as borazole, inorganic benzene, is an inorganic compound with the chemical formula B3H6N3. In this cyclic compound, the three BH units and three NH units alternate. The compound is isoelectronic and isostructural with benzene. For this reason borazine is sometimes referred to as “inorganic benzene”. Like benzene, borazine is a colourless liquid [2] with an aromatic odor.

Contents

Synthesis

The compound was reported in 1926 by the chemists Alfred Stock and Erich Pohland by a reaction of diborane with ammonia. [3]

Borazine can be synthesized by treating diborane and ammonia in a 1:2 ratio at 250–300 °C with a conversion of 50%.

3 B2H6 + 6 NH3 → 2 B3H6N3 + 12 H2

An alternative more efficient route begins with sodium borohydride and ammonium sulfate: [4]

6 NaBH4 + 3 (NH4)2SO4 → 2 B3N3H6 + 3 Na2SO4 + 18 H2

In a two-step process to borazine, boron trichloride is first converted to trichloroborazine:

3 BCl3 + 3 NH4Cl → Cl3B3H3N3 + 9 HCl

The B-Cl bonds are subsequently converted to B-H bonds:

2 Cl3B3H3N3 + 6 NaBH4 → 2 B3H6N3 + 3 B2H6 + 6 NaCl

Structure

Borazine is isoelectronic with benzene and has similar connectivity, so it is sometimes referred to as "inorganic benzene". This comparison is not rigorously valid due to the electronegativity difference between boron and nitrogen. X-ray crystallographic structural determinations show that the bond lengths within the borazine ring are all equivalent at 1.429 Å, a property shared by benzene. [5] However, the borazine ring does not form a perfect hexagon. The bond angle is 117.1° at the boron atoms and 122.9° at the nitrogens, giving the molecule the D3h symmetry point group.

The electronegativity of boron (2.04 on the Pauling scale) compared to that of nitrogen (3.04) and also the electron deficiency on the boron atom and the lone pair on nitrogen favor alternative mesomer structures for borazine.

Borazin Mesomers1.svg

Boron behaves as a Lewis acid and nitrogen behaves as a Lewis base.

Aromaticity

Due to its similarities to benzene, there have been a number of computational and experimental analyses of borazine's aromaticity. The number of pi electrons in borazine obeys the 4n + 2 rule, and the B-N bond lengths are equal, which suggests the compound may be aromatic. The electronegativity difference between boron and nitrogen, however, creates an unequal sharing of charge which results in bonds with greater ionic character, and thus it is expected to have poorer delocalization of electrons than the all-carbon analog. Borazine, with a standard enthalpy change of formation ΔfH of −531 kJ/mol, is thermally very stable.

Natural bond orbitals (NBO)

Natural bond orbital (NBO) analysis suggests weak aromaticity in borazine. [6] In the NBO model, B-N bonds in the ring are slightly displaced from the nuclear axes, and B and N have large differences in charge. Natural chemical shielding (NCS) analysis provides some further evidence for aromaticity based on a contribution of the B-N π bond to magnetic shielding. Computations based on NBO orbitals show that this π bond allows for weak ring current which somewhat counteracts a magnetic field simulated at the center of the borazine ring. A small ring current does suggest some delocalization.

Electron localization function (ELF)

Topological analysis of bonding in borazine by the electron localization function (ELF) indicates that borazine can be described as a π aromatic compound. However, the bonding in borazine is less delocalized than in benzene based on a difference in bifurcation values of the electron basins. Larger bifurcation values indicate better electron delocalization, and it is argued that when this bifurcation value is greater than 0.70, the delocalization is sufficient to designate a compound aromatic. [7] For benzene, this value is 0.91, but the borazine π system bifurcates at the ELF value 0.682. [8] This is caused by the difference in electronegativity between B and N, which produces a weaker bond interaction than the C-C interaction in benzene, leading to increased localization of electrons on the B-H and N-H units. The bifurcation value is slightly below the limit of 0.70 which suggests moderate aromaticity.

Reactivity

Hydrolysis

Borazine hydrolyzes readily, yielding boric acid, ammonia, and hydrogen.

Polymerization

Polyborazylene Polyborazylene Polymer.svg
Polyborazylene

Heating borazine at 70 °C expels hydrogen with formation of polyborazylene:

n B3N3H6 → 1/n[B3N3H4]n

With hydrogen halides and halogens

With hydrogen chloride it forms an adduct.

B3N3H6 + 3 HCl → B3N3H9Cl3
Addition reaction of borazine with hydrogen chloride
B3N3H9Cl3 + NaBH4 → (BH4N)3
Reduction with sodium borohydride

The addition reaction with bromine does not require a catalyst. Borazines undergo nucleophilic attack at boron and electrophilic attack at nitrogen.

Ceramic precursor

Boron nitride can be prepared by heating polyborazylene to 1000 °C. [4]

Borazines are also starting materials for other potential ceramics such as boron carbonitrides. Borazine can also be used as a precursor to grow hexagonal boron nitride (h-BN) thin films and single layers on catalytic surfaces such as copper, [9] platinum, [10] nickel [11] iron [12] and many more, with chemical vapor deposition (CVD).

synthetic route to boron carbonitrides, first step a hydroboration reaction to an oligomeric precursor followed by step two: pyrolysis Boroncaronitrides.svg
synthetic route to boron carbonitrides, first step a hydroboration reaction to an oligomeric precursor followed by step two: pyrolysis

Polyborazylene has been proposed as a recycled hydrogen storage medium for hydrogen fuel cell vehicle applications, using a "single pot" process for digestion and reduction to recreate ammonia borane. [13]

Among other B-N type compounds mixed amino-nitro substituted borazines have been predicted to outperform carbon based explosives such as CL-20. [14] [15]

(C
2
H
2
B
2
N
2
) is a six-membered aromatic ring with two carbon atoms, two nitrogen atoms, and two boron atoms in opposing pairs. [16] [17]

1,2-Dihydro-1,2-azaborine (C
4
BNH
6
) is a six-membered ring with four carbon atoms, one nitrogen atom, and one boron atom.

See also

Further reading

Related Research Articles

<span class="mw-page-title-main">Aromatic compound</span> Compound containing rings with delocalized pi electrons

Aromatic compounds or arenes are organic compounds "with a chemistry typified by benzene" and "cyclically conjugated." The word "aromatic" originates from the past grouping of molecules based on odor, before their general chemical properties were understood. The current definition of aromatic compounds does not have any relation to their odor. Aromatic compounds are now defined as cyclic compounds satisfying Hückel's Rule. Aromatic compounds have the following general properties:

<span class="mw-page-title-main">Covalent bond</span> Chemical bond by sharing of electron pairs

A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms, when they share electrons, is known as covalent bonding. For many molecules, the sharing of electrons allows each atom to attain the equivalent of a full valence shell, corresponding to a stable electronic configuration. In organic chemistry, covalent bonding is much more common than ionic bonding.

<span class="mw-page-title-main">Heterocyclic compound</span> Molecule with one or more rings composed of different elements

A heterocyclic compound or ring structure is a cyclic compound that has atoms of at least two different elements as members of its ring(s). Heterocyclic organic chemistry is the branch of organic chemistry dealing with the synthesis, properties, and applications of organic heterocycles.

<span class="mw-page-title-main">Nitrogen</span> Chemical element with atomic number 7 (N)

Nitrogen is a chemical element; it has symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at seventh in total abundance in the Milky Way and the Solar System. At standard temperature and pressure, two atoms of the element bond to form N2, a colourless and odourless diatomic gas. N2 forms about 78% of Earth's atmosphere, making it the most abundant chemical species in air. Because of the volatility of nitrogen compounds, nitrogen is relatively rare in the solid parts of the Earth.

In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to other atoms were fully ionic. It describes the degree of oxidation of an atom in a chemical compound. Conceptually, the oxidation state may be positive, negative or zero. Beside nearly-pure ionic bonding, many covalent bonds exhibit a strong ionicity, making oxidation state a useful predictor of charge.

<span class="mw-page-title-main">Phenyl group</span> Cyclic chemical group (–C₆H₅)

In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula C6H5, and is often represented by the symbol Ph or Ø. The phenyl group is closely related to benzene and can be viewed as a benzene ring, minus a hydrogen, which may be replaced by some other element or compound to serve as a functional group. A phenyl group has six carbon atoms bonded together in a hexagonal planar ring, five of which are bonded to individual hydrogen atoms, with the remaining carbon bonded to a substituent. Phenyl groups are commonplace in organic chemistry. Although often depicted with alternating double and single bonds, the phenyl group is chemically aromatic and has equal bond lengths between carbon atoms in the ring.

<span class="mw-page-title-main">Conjugated system</span> System of connected p-orbitals with delocalized electrons in a molecule

In theoretical chemistry, a conjugated system is a system of connected p-orbitals with delocalized electrons in a molecule, which in general lowers the overall energy of the molecule and increases stability. It is conventionally represented as having alternating single and multiple bonds. Lone pairs, radicals or carbenium ions may be part of the system, which may be cyclic, acyclic, linear or mixed. The term "conjugated" was coined in 1899 by the German chemist Johannes Thiele.

<span class="mw-page-title-main">Aromaticity</span> Chemical property

In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected by the stabilization of conjugation alone. The earliest use of the term was in an article by August Wilhelm Hofmann in 1855. There is no general relationship between aromaticity as a chemical property and the olfactory properties of such compounds.

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

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

In chemistry, resonance, also called mesomerism, is a way of describing bonding in certain molecules or polyatomic ions by the combination of several contributing structures into a resonance hybrid in valence bond theory. It has particular value for analyzing delocalized electrons where the bonding cannot be expressed by one single Lewis structure. The resonance hybrid is the accurate structure for a molecule or ion; it is an average of the theoretical contributing structures.

<span class="mw-page-title-main">Lewis structure</span> Diagrams for the bonding between atoms of a molecule and lone pairs of electrons

Lewis structures – also called Lewis dot formulas, Lewis dot structures, electron dot structures, or Lewis electron dot structures (LEDs) – are diagrams that show the bonding between atoms of a molecule, as well as the lone pairs of electrons that may exist in the molecule. Introduced by Gilbert N. Lewis in his 1916 article The Atom and the Molecule, a Lewis structure can be drawn for any covalently bonded molecule, as well as coordination compounds. Lewis structures extend the concept of the electron dot diagram by adding lines between atoms to represent shared pairs in a chemical bond.

<span class="mw-page-title-main">Catenation</span> Bonding of atoms of the same element into chains or rings

In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".

In chemistry, a nitride is a chemical compound of nitrogen. Nitrides can be inorganic or organic, ionic or covalent. The nitride anion, N3- ion, is very elusive but compounds of nitride are numerous, although rarely naturally occurring. Some nitrides have a found applications, such as wear-resistant coatings (e.g., titanium nitride, TiN), hard ceramic materials (e.g., silicon nitride, Si3N4), and semiconductors (e.g., gallium nitride, GaN). The development of GaN-based light emitting diodes was recognized by the 2014 Nobel Prize in Physics. Metal nitrido complexes are also common.

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

Tetrasulfur tetranitride is an inorganic compound with the formula S4N4. This vivid orange, opaque, crystalline explosive is the most important binary sulfur nitride, which are compounds that contain only the elements sulfur and nitrogen. It is a precursor to many S-N compounds and has attracted wide interest for its unusual structure and bonding.

<span class="mw-page-title-main">Cyclic compound</span> Molecule with a ring of bonded atoms

A cyclic compound is a term for a compound in the field of chemistry in which one or more series of atoms in the compound is connected to form a ring. Rings may vary in size from three to many atoms, and include examples where all the atoms are carbon, none of the atoms are carbon, or where both carbon and non-carbon atoms are present. Depending on the ring size, the bond order of the individual links between ring atoms, and their arrangements within the rings, carbocyclic and heterocyclic compounds may be aromatic or non-aromatic; in the latter case, they may vary from being fully saturated to having varying numbers of multiple bonds between the ring atoms. Because of the tremendous diversity allowed, in combination, by the valences of common atoms and their ability to form rings, the number of possible cyclic structures, even of small size numbers in the many billions.

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

Boron compounds are compounds containing the element boron. In the most familiar compounds, boron has the formal oxidation state +3. These include oxides, sulfides, nitrides, and halides.

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

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

Hexazine is a hypothetical allotrope of nitrogen composed of 6 nitrogen atoms arranged in a ring-like structure analogous to that of benzene. As a neutrally charged species, it would be the final member of the azabenzene (azine) series, in which all of the methine groups of the benzene molecule have been replaced with nitrogen atoms. The two last members of this series, hexazine and pentazine, have not been observed, although all other members of the azine series have.

<span class="mw-page-title-main">Boroxine</span> 6-sided cyclic compound of oxygen and boron

Boroxine is a 6-membered heterocyclic compound composed of alternating oxygen and singly-hydrogenated boron atoms. Boroxine derivatives such as trimethylboroxine and triphenylboroxine also make up a broader class of compounds called boroxines. These compounds are solids that are usually in equilibrium with their respective boronic acids at room temperature. Beside being used in theoretical studies, boroxine is primarily used in the production of optics.

Carborazine is a six-membered aromatic ring with two carbon atoms, two nitrogen atoms and two boron atoms in opposing pairs.

References

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Further reading

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