Boron monohydride

Last updated
Boron monohydride
Boron monohydride.png
Names
IUPAC name
λ1-borane
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
33
PubChem CID
  • InChI=1S/BH/h1H
    Key: UWBOAQKPEXKXSU-UHFFFAOYSA-N
  • DB:InChI=1S/BH/h1H/i1D
    Key: UWBOAQKPEXKXSU-MICDWDOJSA-N
  • TB:InChI=1S/BH/h1H/i1T
    Key: UWBOAQKPEXKXSU-CNRUNOGKSA-N
  • BH:[BH]
  • DB:[2H][B]
  • TB:[3H][B]
Properties
BH
Molar mass 11.82 g·mol−1
Thermochemistry [1]
Std molar
entropy
(S298)
172
442.7
412.7
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Borane(1), boron monohydride, hydridoboron or borylene is the molecule with the formula BH. It exists as a gas but rapidly degrades when condensed. By contrast, the cluster B12H122- (dodecaborate), which has very similar empirical formula, forms robust salts.

Contents

Formation

Boron monohydride can be formed from borane carbonyl exposed to ultraviolet light. BH3CO → BH + CH2O [2]

Boron monohydride is formed when boron compounds are heated to a high temperature in the presence of hydrogen. [3]

Boron monohydride is formed when the boron anion B reacts with a hydrogen ion H+. It is also formed when atomic boron reacts with hydrogen. B + H2 → BH + H. There is too much energy in the reaction for BH2 to be stable. [4]

Boron monohydride probably exists in sunspots, [5] but as of 2008 has not been detected. [6]

Properties

The ionization potential is around 9.77  eV. [7] The dissociation energy for the ground state molecule is 81.5 kcal/mol. [8] The electron affinity is roughly 0.3 eV, and the HB ion is formed. [9]

The dipole moment of the molecule in its ground state is 1.27 debye and for the first excited electronic state A1Π is 0.58 debye. [10]

The spectrum of boron monohydride includes a molecular band for the lowest electronic transition X1Σ+ → A1Π with a band head at 433.1 nm (for 0→0) and 437.1 (for 0→1) [3] The spectrum contains P, Q, and R branches. [10]

Although BH is a closed shell molecule, it is paramagnetic independent of temperature. [11]

Reactions

Boron monohydride is unstable in bulk and disappears quickly on a timescale of 20 ns when at a pressure of 20 Torr. [12] Boron monohydride reacts with oxygen, probably forming HBO. [2] Boron monohydride shows no reaction with methane, but reacts with propane to give C3H7BH2. With nitric oxide (NO) it probably yields HBO and HBNO. Boron monohydride appears to add onto double bonds in unsaturated organic compounds. It also reacts with water. [2]

Boron monohydride can take on the form of solid poly-borane(1) which spontaneously inflames in air. [13]

Solid BH is predicted to take on an Ibam phase at pressures over 50 GPa and then become a metallic P6/mmm phase over 168 GPa. [14]

Ions

Both a cation and a dication are known. The dication HB2+ can be supported by a σ-donating ligand framework with two links. [15] The dianion can also be stabilized by an amine. [16]

Related Research Articles

In chemistry, hydronium is the cation [H3O]+, also written as H3O+, the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is dissolved in water, as Arrhenius acid molecules in solution give up a proton to the surrounding water molecules. In fact, acids must be surrounded by more than a single water molecule in order to ionize, yielding aqueous H+ and conjugate base.

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

Boron hydride clusters are compounds with the formula BxHy or related anions, where x ≥ 3. Many such cluster compounds are known. Common examples are those with 5, 10, and 12 boron atoms. Although they have few practical applications, the borane hydride clusters exhibit structures and bonding that differs strongly from the patterns seen in hydrocarbons. Hybrids of boranes and hydrocarbons, the carboranes are also well developed.

<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.

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

Ammonia borane, also called borazane, is the chemical compound with the formula H3NBH3. The colourless or white solid is the simplest molecular boron-nitrogen-hydride compound. It has attracted attention as a source of hydrogen fuel, but is otherwise primarily of academic interest.

<span class="mw-page-title-main">Methanium</span> Ion of carbon with five hydrogens

In chemistry, methanium is a complex positive ion with formula [CH5]+ or [CH3(H2)]+, bearing a +1 electric charge. It is a superacid and one of the onium ions, indeed the simplest carbonium ion.

<span class="mw-page-title-main">Positronium hydride</span> Exotic molecule consisting of a hydrogen atom bound to a positronium atom

Positronium hydride, or hydrogen positride is an exotic molecule consisting of a hydrogen atom bound to an exotic atom of positronium. Its formula is PsH. It was predicted to exist in 1951 by A Ore, and subsequently studied theoretically, but was not observed until 1990. R. Pareja, R. Gonzalez from Madrid trapped positronium in hydrogen laden magnesia crystals. The trap was prepared by Yok Chen from the Oak Ridge National Laboratory. In this experiment the positrons were thermalized so that they were not traveling at high speed, and they then reacted with H ions in the crystal. In 1992 it was created in an experiment done by David M. Schrader and F.M. Jacobsen and others at the Aarhus University in Denmark. The researchers made the positronium hydride molecules by firing intense bursts of positrons into methane, which has the highest density of hydrogen atoms. Upon slowing down, the positrons were captured by ordinary electrons to form positronium atoms which then reacted with hydrogen atoms from the methane.

A frustrated Lewis pair (FLP) is a compound or mixture containing a Lewis acid and a Lewis base that, because of steric hindrance, cannot combine to form a classical adduct. Many kinds of FLPs have been devised, and many simple substrates exhibit activation.

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

Thiophosphoryl fluoride is an inorganic molecular gas with formula PSF3 containing phosphorus, sulfur and fluorine. It spontaneously ignites in air and burns with a cool flame. The discoverers were able to have flames around their hands without discomfort, and called it "probably one of the coldest flames known". The gas was discovered in 1888.

<span class="mw-page-title-main">Chromium(I) hydride</span> Chemical compound

Chromium(I) hydride, systematically named chromium hydride, is an inorganic compound with the chemical formula (CrH)
n
. It occurs naturally in some kinds of stars where it has been detected by its spectrum. However, molecular chromium(I) hydride with the formula CrH has been isolated in solid gas matrices. The molecular hydride is very reactive. As such the compound is not well characterised, although many of its properties have been calculated via computational chemistry.

Borane, also known as borine, is an unstable and highly reactive molecule with the chemical formula BH
3
. The preparation of borane carbonyl, BH3(CO), played an important role in exploring the chemistry of boranes, as it indicated the likely existence of the borane molecule. However, the molecular species BH3 is a very strong Lewis acid. Consequently, it is highly reactive and can only be observed directly as a continuously produced, transitory, product in a flow system or from the reaction of laser ablated atomic boron with hydrogen. It normally dimerizes to diborane in the absence of other chemicals.

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

Calcium monohydride is a molecule composed of calcium and hydrogen with formula CaH. It can be found in stars as a gas formed when calcium atoms are present with hydrogen atoms.

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

Magnesium monohydride is a molecular gas with formula MgH that exists at high temperatures, such as the atmospheres of the Sun and stars. It was originally known as magnesium hydride, although that name is now more commonly used when referring to the similar chemical magnesium dihydride.

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

The dodecaborate(12) anion, [B12H12]2−, is a borane with an icosahedral arrangement of 12 boron atoms, with each boron atom being attached to a hydrogen atom. Its symmetry is classified by the molecular point group Ih.

<span class="mw-page-title-main">1,2-Dimethyldiborane</span> Chemical compound

1,2-Dimethyldiborane is an organoboron compound with the formula [(CH3)BH2]2. Structurally, it is related to diborane, but with methyl groups replacing terminal hydrides on each boron. It is the dimer of methylborane, CH3BH2, the simplest alkylborane. 1,2-Dimethyldiborane can exist in a cis- and a trans arrangement. 1,2-Dimethyldiborane is an easily condensed, colorless gas that ignites spontaneously in air.

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

Dimethylborane, (CH3)2BH is the simplest dialkylborane, consisting of a methyl group substituted for a hydrogen in borane. As for other boranes it normally exists in the form of a dimer called tetramethyldiborane or tetramethylbisborane or TMDB ((CH3)2BH)2. Other combinations of methylation occur on diborane, including monomethyldiborane, trimethyldiborane, 1,2-dimethylborane, 1,1-dimethylborane and trimethylborane. At room temperature the substance is at equilibrium between these forms. The methylboranes were first prepared by H. I. Schlesinger and A. O. Walker in the 1930s.

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

Trimethyldiborane, (CH3)3B2H3 is a molecule containing boron carbon and hydrogen. It is an alkylborane, consisting of three methyl group substituted for a hydrogen in diborane. It can be considered a mixed dimer: (CH3)2BH2BH(CH3) or dimethylborane and methylborane. called 1,2-dimethyldiborane. Other combinations of methylation occur on diborane, including monomethyldiborane, 1,2-dimethyldiborane, tetramethyldiborane, 1,1-dimethylborane and trimethylborane. At room temperature the substance is at equilibrium between these forms, so it is difficult to keep it pure. The methylboranes were first prepared by H. I. Schlesinger and A. O. Walker in the 1930s.

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

Methyldiborane, CH3B2H5, or monomethyldiborane is the simplest of alkyldiboranes, consisting of a methyl group substituted for a hydrogen in diborane. As with other boranes it exists in the form of a dimer with a twin hydrogen bridge that uses three-center two-electron bonding between the two boron atoms, and can be imagined as methyl borane (CH3BH2) bound to borane (BH3). Other combinations of methylation occur on diborane, including 1,1-dimethylborane, 1,2-dimethyldiborane, trimethyldiborane, tetramethyldiborane, and trimethylborane (which is not a dimer). At room temperature the substance is at equilibrium between these molecules.

Diborane(2), also known as diborene, is an inorganic compound with the formula B2H2. The number 2 in diborane(2) indicates the number of hydrogen atoms bonded to the boron complex. There are other forms of diborane with different numbers of hydrogen atoms, including diborane(4) and diborane(6).

<span class="mw-page-title-main">1,1-Dimethyldiborane</span> Chemical compound

1,1-Dimethyldiborane is the organoboron compound with the formula (CH3)2B(μ-H)2BH2. A pair of related 1,2-dimethyldiboranes are also known. It is a colorless gas that ignites in air.

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

The triboracyclopropenyl fragment is a cyclic structural motif in boron chemistry, named for its geometric similarity to cyclopropene. In contrast to nonplanar borane clusters that exhibit higher coordination numbers at boron (e.g., through 3-center 2-electron bonds to bridging hydrides or cations), triboracyclopropenyl-type structures are rings of three boron atoms where substituents at each boron are also coplanar to the ring. Triboracyclopropenyl-containing compounds are extreme cases of inorganic aromaticity. They are the lightest and smallest cyclic structures known to display the bonding and magnetic properties that originate from fully delocalized electrons in orbitals of σ and π symmetry. Although three-membered rings of boron are frequently so highly strained as to be experimentally inaccessible, academic interest in their distinctive aromaticity and possible role as intermediates of borane pyrolysis motivated extensive computational studies by theoretical chemists. Beginning in the late 1980s with mass spectrometry work by Anderson et al. on all-boron clusters, experimental studies of triboracyclopropenyls were for decades exclusively limited to gas-phase investigations of the simplest rings (ions of B3). However, more recent work has stabilized the triboracyclopropenyl moiety via coordination to donor ligands or transition metals, dramatically expanding the scope of its chemistry.

References

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  3. 1 2 Abad, Carlos; Florek, Stefan; Becker-Ross, Helmut; Huang, Mao-Dong; Heinrich, Hans-Joachim; Recknagel, Sebastian; Vogl, Jochen; Jakubowski, Norbert; Panne, Ulrich (October 2017). "Determination of boron isotope ratios by high-resolution continuum source molecular absorption spectrometry using graphite furnace vaporizers". Spectrochimica Acta Part B: Atomic Spectroscopy. 136: 116–122. Bibcode:2017AcSpB.136..116A. doi:10.1016/j.sab.2017.08.012.
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