Tetraborane - Wikipedia 14/01/2018, 20)42

Tetraborane
Tetraborane (systematically named arachno-tetraborane(10)) was
the first boron hydride compound to be classified by Stock and Messenez
Tetraborane
in 1912 and was first isolated by Alfred Stock. It has a relatively low
boiling point at 18 °C and is a gas at room temperature. Tetraborane gas is
foul smelling and toxic.

Contents
History
Structure
Names
Isomers
IUPAC names
Safety
tetraborane(10)
Preparation arachno-B4H10
References
Identifiers
External links
CAS Number 18283-93-7 (http://w
ww.commonchemistr
History y.org/ChemicalDetail.
aspx?ref=18283-93-
The class of boranes was elucidated using x-ray diffraction analysis by 7)
Lipscomb et. Al. in the 1950s. The x-ray data showed they have 2-electron
ChEBI CHEBI:33592 (https:/
multicenter bonds. Later, analysis based on high-resolution x-ray data
/www.ebi.ac.uk/chebi
was performed to analyze the charge-density.[2] The comparison of the
/searchId.do?chebiId
diffraction data from x-ray diffraction and electron-diffraction gave
=33592)
suspected bond lengths: B1—B2=1.84 A, B1—B3= 1.71 A, <B2B1B4= 98 ̊, B
—H=1.19 A, B1—Hµ= 1.33 A, B2—Hµ=1.43 A.[3] ChemSpider 21865171 (http://ww
w.chemspider.com/C
Structure hemical-Structure.21
865171.html)
The “parent” structure of boranes is referred to as closo, but when the
InChI
second and third vertices are removed the new structure is B4H10 and
referred to as arachno. Properties[1]
Chemical B4H10
formula
Molar mass 53.32 g/mol
Appearance colourless gas
Density 2.3 kg m−3 (gas)

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Type formula notes Melting point −120.8 °C

(−185.4 °F; 152.3 K)
closo− BnHn2− No neutral BnHn+2 boranes are known
Boiling point 18 °C (64 °F; 291 K)
nido− BnHn+4
Except where otherwise noted, data
arachno− BnHn+6 are given for materials in their
standard state (at 25 °C [77 °F],
hypho− BnHn+8 only adducts established 100 kPa).

Boron is often called “electron deficient,” because it has three valence

verify (what is ?)
electrons, and the standard, carbon, has four. In reality the Boron is Infobox references
stable, and is no way actually deficient of electrons. To solve the issue of
“deficiency” the hydrogen bridge or protonated double bonds are introduced to the structure.[4] Each boron is sp3
hybridized and “the configuration of the three hydrogens surrounding borons B1 and B3 is approximately trigonal and
suggests approximately tetrahedral hybridization for these borons which would predict bond angles of 120.” However,
the Boron arrangements can be classified as fragments of either the icosahedron or the octahedron because the bond
angles are actually between 105 ̊ and 90 ̊.[5] The bonding produces a butterfly geometry in the arachno structure. The
Polyhedral Skeletal Electron Pair Theory (PSEPT), originally discovered by Kenneth Wade, are often referred to as
Wade’s rules. These rules can be used to count electrons in structures, such as boron hydrides.[6]

Isomers
Scientists are currently working to produce the bis(diboranyl) isomer of the arachno-tetraborane structure. The
bis(diboranyl) is expected to have a lower energy at the Hartree-Fock method (HF) level. By using Wurtz reaction or
coupling of B2H5I in the presence of the sodium amalgam, scientists believe they have produced the bis(diboranyl)
isomer. Once the isomer was created, they tried to discover the mechanism that could then be used to turn the isomer
into the arachno-tetraborane structure. Instead of discovering the mechanism, three different pathways have been
constructed.

Path 1: Similar to the dissociative pathway to B3H7 and BH3 proposed by McKee

Path 2: Concerted pathway over two transition states separated by a local minimum and is
different than those suggested by McKee

Path 3: Involves the penta-coordinated isomers as intermediates… also a concerted

pathway

Path two and three are more likely, because they are more energetically favored with energies of 33.1 kcal/mol and
22.7 kcal/mol respectively.[7]

Safety
Because it is easily oxidized it must be kept under vacuum. Tetraborane ignites when it comes in contact with air,
oxygen, and nitric acid. Boranes in general including tetraborane have been deemed very toxic and are biologically
destructive. A study consisting of small daily exposure of the chemical to rabbits and rats resulted in fatality.[8]

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Preparation
Tetraborane can be produced via a reaction between acid and magnesium, aluminum, or beryillium borides.
Hydrolysis of magnesium boride, hydrogenation of boron halide (at high temperatures) and the pyrolysis of diborane
also produce tetraborane. The hydrolysis of magnesium boride was one of the first reactions to give a high yield(14%)
of tetraborane. Phosphoric acid proved to be the most efficient acid (other than hydrochloric and sulfuric acid) in the
reaction with magnesium boride. Reduction of boron halides with hydrogen in the presence of metal hydride at high
temperatures also produces tetraborane[9]

References
1. Weast, Robert C., ed. (1981). CRC Handbook of Chemistry and Physics (62nd ed.). Boca Raton, FL: CRC Press.
p. B-84. ISBN 0-8493-0462-8.
2. 5. Forster, Diana. et. Al. (2007). Inorg. Chem. “On the 2-Electron 3-Center B—H—B Bond: Charge Density
Determination of Tetraborane(10).”
3. 6. Lipscomb, William N. Boron Hydrides. New York: W. A. Benjamin, 1963. Print.
4. Grimes, Russel N. "Boron." Advanced Inorganic Chemistry. By F. Albert Cotton, Geoffrey Wilkinson, Carlos A.
Murillo, and Manfred Bochmann. 6th ed. N.p.: n.p., 1999. 143-46. Print.
5. Lipscomb, William N. Boron Hydrides. New York: W. A. Benjamin, 1963. Print.
6. Grimes, Russel N. "Boron." Advanced Inorganic Chemistry. By F. Albert Cotton, Geoffrey Wilkinson, Carlos A.
Murillo, and Manfred Bochmann. 6th ed. N.p.: n.p., 1999. 143-46. Print.
7. Ramakrishna, Vinutha and Duke, Brian J. (2004). Inorg. Chem. “Can the Bis(diboranyl) Structure of B4H10 Be
Observed? The Story Continues.”
8. "Archived copy" (https://web.archive.org/web/20110727012047/http://voh.chem.ucla.edu/vohtar/spring05/classes/
172/pdf/p21-30Borane.pdf) (PDF). Archived from the original (http://voh.chem.ucla.edu/vohtar/spring05/classes/1
72/pdf/p21-30Borane.pdf) (PDF) on 2011-07-27. Retrieved 2011-05-11.
9. Dain, C. J.; Downs, A. J.; Laurenson, G. S.; Rankin, D. W. H. (1981). "The Molecular Structure of Tetraborane(10)
in the Gas Phase as determined by a Joint Analysis of Electron-diffraction and Microwave Data". Journal of the
Chemical Society, Dalton Transactions. 1981 (2): 472–477. doi:10.1039/DT9810000472 (https://doi.org/10.1039%
2FDT9810000472).

External links
"Boron»tetraborane (10) [WebElements Periodic Table]" (http://www.webelements.com/compounds/boron/tetrabo
rane_10.html). Webelements.com. Retrieved 2017-06-07.
"Linus Pauling Research Notebooks - Special Collections & Archives Research Center" (http://osulibrary.orst.edu/
specialcollections/rnb/23/23-184.html). Osulibrary.orst.edu. Retrieved 2017-06-07.

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