Boroxine () is a 6-membered
heterocyclic compound
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, proper ...
composed of alternating
oxygen
Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...
and singly-hydrogenated
boron
Boron is a chemical element; it has symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the boron group it has three ...
atoms. Boroxine
derivatives (boronic
anhydride
An acid anhydride is a type of chemical compound derived by the removal of water molecules from an acid (chemistry), acid.
In organic chemistry, organic acid anhydrides contain the functional group . Organic acid anhydrides often form when one ...
s) such as trimethylboroxine and triphenylboroxine also make up a broader class of compounds called boroxines.
[Brown, H.C. ''Boranes in Organoc Chemistry''; Cornell University Press: Ithaca, 1972; pp. 346–347.] These compounds are solids that are usually in equilibrium with their respective
boronic acids at room temperature.
[Hall, Dennis G. (2005)]
Boronic Acids – Preparation and Applications in Organic Synthesis and Medicine
John Wiley & Sons . Beside being used in theoretical studies, boroxine is primarily used in the production of optics.
Structure and bonding
Three-coordinate compounds of boron typically exhibit trigonal planar geometry, therefore the boroxine ring is locked in a planar geometry as well.
[Onak, T. in ''Organoborane Chemistry''; Maitles, P.M., Stone, F.G.A., West, R., Eds.; Academic Press: New York, 1975; pp. 2,4,16,44.] These compounds are isoelectronic to
benzene
Benzene is an Organic compound, organic chemical compound with the Chemical formula#Molecular formula, molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar hexagonal Ring (chemistry), ring with one hyd ...
. With the vacant p-orbital on the boron atoms, they may possess some aromatic character.
Boron single-bonds on boroxine compounds are mostly s-character.
Ethyl-substituted boroxine has B-O bond lengths of 1.384 Å and B-C bond lengths of 1.565 Å.
Phenyl-substituted boroxine has similar bond lengths of 1.386 Å and 1.546 Å respectively, showing that the substituent has little effect on the boroxine ring size.
Substitutions onto a boroxine ring determine its crystal structure. Alkyl-substituted boroxines have the simplest crystal structure. These molecules stack on top of each other, aligning an oxygen atom from one molecule with a boron atom in another, leaving each boron atom between two other oxygen atoms. This forms a tube out of the individual boroxine rings. The intermolecular B-O distance of ethyl-substituted boroxine is 3.462 Å, which is much longer than the B-O bond distance of 1.384 Å. The crystal structure of phenyl-substituted boroxine is more complex. The interaction between the vacant p-orbitals in the boron atoms and the π-electrons in the aromatic, phenyl-substituents cause a different crystal structure. The boroxine ring of one molecule is stacked between two phenyl rings of other molecules. This arrangement allows the phenyl-substituents to donate π-electron density to the vacant boron p-orbitals.
Synthesis
The parent boroxine (''cyclo''-(HBO)
3) is prepared in small quantities as a low pressure gas by high temperature reaction of water and elemental boron or reaction of various
boranes
A borane is a compound with the formula although examples include multi-boron derivatives. A large family of boron hydride clusters is also known. In addition to some applications in organic chemistry, the boranes have attracted much attention ...
(B
2H
6 or B
5H
9) with O
2. It is thermodynamically unstable with respect to disproportionation to diborane and boron oxide. Some reactivity studies and an IR spectrum are reported, but it is otherwise not well characterized.
As discovered in the 1930s, substituted boroxines (''cyclo''-(RBO)
3, R = alkyl or aryl) are generally produced from their corresponding boronic acids by dehydration.
This dehydration can be done either by a drying agent or by heating under a high vacuum.
Boroxine can also be produced by using mechanochemistry and trimethylbroxine, which avoids the use of ball milling materials. The trimethylbroxine appears to shift the equilibrium of the reaction as a dehydrating agent and facilitates the growth of COF material.
Trimethylboroxine can be synthesized by reacting
carbon monoxide
Carbon monoxide (chemical formula CO) is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the si ...
with
diborane
Diborane(6), commonly known as diborane, is the chemical compound with the formula . 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 att ...
(B
2H
6) and
lithium borohydride
Lithium borohydride (LiBH4) is a borohydride and known in organic synthesis as a reducing agent for esters. Although less common than the related sodium borohydride, the lithium salt offers some advantages, being a stronger reducing agent and ...
(LiBH
4) as a catalyst (or reaction of
borane–tetrahydrofuran or
borane–(dimethyl sulfide) in the presence of
sodium borohydride
Sodium borohydride, also known as sodium tetrahydridoborate and sodium tetrahydroborate, is an inorganic compound with the formula (sometimes written as ). It is a white crystalline solid, usually encountered as an aqueous basic solution. Sodi ...
):
:
:
Reactions
Trimethylboroxine is used in the methylation of various aryl halides through
palladium
Palladium is a chemical element; it has symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1802 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas (formally 2 Pallas), ...
-catalyzed
Suzuki-Miyaura coupling reactions:
:
\overset + (CH3BO)3 -> ce\ce] C6H5CH3
Another form of the Suzuki-Miyaura
coupling reaction
In organic chemistry, a coupling reaction is a type of reaction in which two reactant molecules are bonded together. Such reactions often require the aid of a metal catalyst. In one important reaction type, a main group organometallic compound o ...
exhibits selectivity to aryl chlorides:
:

Boroxines have also been examined as precursors to monomeric
oxoborane, HB≡O.
This compound quickly converts back to the cyclic boroxine, even at low temperatures.
References
{{reflist
Boron heterocycles
Inorganic compounds
Six-membered rings