Tetramethyldiborane

Last updated
Tetramethyldiborane
Tetramethyldiborane.svg
Names
IUPAC name
Tetramethyldiborane(6)
Other names
Dimethylborane dimer
Identifiers
3D model (JSmol)
  • InChI=1S/C4H14B2/c1-5(2)7-6(3,4)8-5/h1-4H3
    Key: DAOILNUAERZCST-UHFFFAOYSA-N
  • InChI=1/C4B2H14/c1-5(2)7-6(3,4)8-5/h1-4H3
  • C[B]1(C)[H][B](C)(C)[H]1
Properties
(CH
3)
2BH
2B(CH
3)
2
Molar mass 83.777
AppearanceColorless liquid
Odor Pungent;
Melting point −72.5 °C (−98.5 °F; 200.7 K)
Boiling point 68.6 °C (155.5 °F; 341.8 K)
Hazards
NFPA 704 (fire diamond)
[1]
NFPA 704.svgHealth (blue): no hazard codeFlammability 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 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
2
2
Related compounds
Related alkyl boranes
trimethylborane
dimethyldiborane
diethylborane
Related compounds
 Borane
tetramethyl aluminium hydride
tetramethyl gallium hydride

methylalane

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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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. [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. [3] The methylboranes were first prepared by H. I. Schlesinger and A. O. Walker in the 1930s. [4] [5]

Contents

Properties

Tetramethyldiborane has two boron atoms linked by a two hydrogen atom bridge, and each boron is linked to two methyl groups. A tetramethyldiborane molecule belongs to the D2h point group. Its infrared spectrum shows a strong absorption band at 1602 cm−1 due to bridging hydrogen, a weak band at 1968 cm−1 and lines due to methyl between 900 and 1400 cm−1. [6] In the molecule the boron to hydrogen distance is 1.36 Å, the boron to boron distance is 1.84 Å; the boron to carbon distance is 1.590 Å; the angle of boron-boron to carbon is 120.0°; the boron-carbon-hydrogen angle is 112.0°. [7] The NMR J coupling between two boron-11 nuclei in tetramethyldiborane is 55 Hz. [8]

Tetramethyldiborane melts at −72.5 °C and boils at 68.6 °C. [9] Vapour pressure is approximated by Log P = 7.687−(1643/T). [9] Tetramethyldiborane has a vapour pressure of 48 mm Hg at 0 °C. [10] Heat of vapourisation was measured at 7.3 kcal/mol. [11] The predicted heat of formation for the liquid is ΔH0f=−65 kcal/mol, and for the gas −57 kcal/mol. [11]

A gas chromatograph can be used to determine the amounts of the methyl boranes in a mixture. The order they pass through are diborane, monomethyldiborane, trimethylborane, 1,1-dimethyldiborane, 1,2-dimethyldiborane, trimethyldiborane, and lastly tetramethyldiborane. [12]

The nuclear resonance shift for the bridge hydrogen is 8.90 ppm, compared to 10.49 for diborane. [13]

Preparation

Dimethylborane is formed when lithium dimethylborohydride Li(CH3)2BH2 reacts with an acid. [14] The lithium dimethylborohydride can be made from a dimethylborinic ester and lithium monoethoxy aluminium hydride. [14]

Methylboranes are also formed by the reaction of diborane and trimethylborane. This reaction produces four different substitutions of methyl with hydrogen on diborane. Produced is 1-methyldiborane, 1,1-dimethyldborane, 1,1,2-trimethyldiborane and 1,1,2,2-tetramethyldiborane. [3] The latter is maximised when trimethylborane is six times the concentration of diborane. [10]

Other methods to form methyldiboranes include reacting hydrogen with trimethylborane between 80 and 200 °C under pressure, or reacting a metal borohydride with trimethylborane in the presence of hydrogen chloride, aluminium chloride or boron trichloride. If the borohydride is sodium borohydride, then methane is a side product. If the metal is lithium then no methane is produced. [4] dimethylchloroborane and methyldichloroborane are also produced as gaseous products. [4]

Atomic hydrogen converts trimethylborane on a graphene monolayer surface to dimethylborane which dimerises to tetramethyldiborane. [15]

Reactions

Dimethylborane reacts with alkenes with the highest yield in ether to produce a dimethylalkylborane. [14] The dimethylalkylboranes can then be converted to a tertiary alcohol by oxidative carbonylation. This requires heating to 150° with carbon monoxide under 50 bars of pressure, and then oxidation with hydrogen peroxide. [16]

Methylboranes such as tetramethyldiborane disproportionate in the gas phase to trimethylborane and diborane at room temperature. [3] The time period is on the order of a few hours, and disproportionation is faster the higher the temperature. [4] At 0 °C disproportionation takes about a day. [4] At −78.5 °C methyldiborane disproportionates slowly first to diborane and 1,1-dimethyldiborane. [17] In solution methylborane is more stable against disproportionation than dimethylborane. [14]

4(CH3)3B2H3⇌ (CH3)4B2H2 + B2H6 K=0.0067. [18]
3B2H2Me4⇌ 2 B2H3Me3 + 2 BMe3

Dimethylborane is hydrolyzed in water to Dimethylborinic acid (CH3)2BOH. [3]

Dimethyldiborane spontaneously inflames when exposed to air. [17]

Ammonia and tetramethyldiborane combine to form a white solid at −78 °C. The solid decomposes above 10 °C. [19] The structure of the solid is ionic [(CH3)2B(NH3)2]+ [(CH3)2BH2]−. [19] [20] A simple adduct BHMe3.NH3 is formed from tetramethyldiborane and ammonia in ether. This also forms during the thermal decomposition of the diammoniate. [21]

Acetonitrile reacts slowly with tetramethyldiborane at room temperature to form dimeric ethylideneaminodimethylborane (CH3CH=NB(CH3)2)2. This has a cis and a trans isomer, one melting at 76 °C and another at −5 °C. [22]

Tetramethyldiborane reacts with sodium in liquid ammonia to make a salt with formula Na2HB(CH3)2 called sodium dimethylboryl. The salt is white and stable to 90 °C. [21] With potassium K2HB(CH3)2 potassium dimethylboryl is formed. [23] Calcium metal react with tetramethyldiborane to make CaHB(CH3)2.NH3. [21]

Tetramethyldiborane combines with dimethylphosphine to yield an adduct of dimethylborane. [21]

Tetramethyldiborane reacts with organic borates to form methylboronic esters.

2 (CH3)4B2H2 + 4 B(OR)3⇌ 6 CH3(OR)2 + (CH3)2B2H4. [24]

Tetramethyldiborane acts as a catalyst to enable the same results from trimethylborane:

(CH3)3B + 2 B(OR)3 → 3 CH3(OR)2 [24]

The tetramethylborate anion (CH3)4B− only has one boron atom. [25]

Related Research Articles

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H−), a hydrogen ion with two electrons. In modern usage, this is typically only used for ionic bonds, but it is sometimes (and more frequently in the past) been applied to all compounds containing covalently bound H atoms. In this broad and potentially archaic sense, water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. In covalent compounds, it implies hydrogen is attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

Hydroboration–oxidation reaction is a two-step hydration reaction that converts an alkene into an alcohol. The process results in the syn addition of a hydrogen and a hydroxyl group where the double bond had been. Hydroboration–oxidation is an anti-Markovnikov reaction, with the hydroxyl group attaching to the less-substituted carbon. The reaction thus provides a more stereospecific and complementary regiochemical alternative to other hydration reactions such as acid-catalyzed addition and the oxymercuration–reduction process. The reaction was first reported by Herbert C. Brown in the late 1950s and it was recognized in his receiving the Nobel Prize in Chemistry in 1979.

<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">Herbert C. Brown</span> American chemist (1912–2004)

Herbert Charles Brown was an American chemist and recipient of the 1979 Nobel Prize in Chemistry for his work with organoboranes.

<span class="mw-page-title-main">Organoboron chemistry</span> Study of compounds containing a boron-carbon bond

Organoboron chemistry or organoborane chemistry studies organoboron compounds, also called organoboranes. These chemical compounds combine boron and carbon; typically, they are organic derivatives of borane (BH3), as in the trialkyl boranes.

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

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 with an aromatic odor.

In organic chemistry, hydroboration refers to the addition of a hydrogen-boron bond to certain double and triple bonds involving carbon. This chemical reaction is useful in the organic synthesis of organic compounds.

<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 for hydrogen fuel, but is otherwise primarily of academic interest.

<span class="mw-page-title-main">Borohydride</span> Any chemical compound having a borohydride anion

Borohydride refers to the anion [BH4]−, which is also called tetrahydridoborate, and its salts. Borohydride or hydroborate is also the term used for compounds containing [BH4−nXn]−, where n is an integer from 0 to 3, for example cyanoborohydride or cyanotrihydroborate [BH3(CN)]− and triethylborohydride or triethylhydroborate [BH(CH2CH3)3]−. Borohydrides find wide use as reducing agents in organic synthesis. The most important borohydrides are lithium borohydride and sodium borohydride, but other salts are well known. Tetrahydroborates are also of academic and industrial interest in inorganic chemistry.

<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.

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

Beryllium hydride is an inorganic compound with the chemical formula n. This alkaline earth hydride is a colourless solid that is insoluble in solvents that do not decompose it. Unlike the ionically bonded hydrides of the heavier Group 2 elements, beryllium hydride is covalently bonded.

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

Trimethylborane (TMB) is a toxic, pyrophoric gas with the formula B(CH3)3 (which can also be written as Me3B, with Me representing methyl).

Borane is an inorganic compound with the chemical formula BH
3. Because it tends to dimerize or form adducts, borane is very rarely observed. It normally dimerizes to diborane in the absence of other chemicals. It can be observed directly as a continuously produced, transitory, product in a flow system or from the reaction of laser ablated atomic boron with hydrogen.

<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">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.

<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.

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<span class="mw-page-title-main">Boranes</span> Class of chemical compounds

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References

  1. ↑ Baker, Charles J. (2001). The Fire Fighter's Handbook of Hazardous Materials. Jones & Bartlett Learning. p. 352. ISBN   9780962705212.
  2. ↑ Srebnik, Morris; Cole, Thomas E.; Brown, Herbert C. (January 1987). "Methylborane - a remarkable unhindered monoalkylborane which achieves the controlled sequential hydroboration of representative alkenes". Tetrahedron Letters. 28 (33): 3771–3774. doi:10.1016/s0040-4039(00)96380-9.
  3. 1 2 3 4 Bell, R. P.; Emeléus, H. J. (1948). "The boron hydrides and related compounds". Quarterly Reviews, Chemical Society. 2 (2): 132. doi:10.1039/QR9480200132.
  4. 1 2 3 4 5 Long, L. H.; Wallbridge, M. G. H. (1965). "646. The chemistry of boron. Part VI. New preparative methods and decomposition studies relating to methyldiboranes". Journal of the Chemical Society (Resumed): 3513–3520. doi:10.1039/JR9650003513.(subscription required)
  5. ↑ Schlesinger, H. I.; Walker, A. O. (April 1935). "Hydrides of Boron. IV. The Methyl Derivatives of Diborane". Journal of the American Chemical Society. 57 (4): 621–625. doi:10.1021/ja01307a009.
  6. ↑ Cowan, R. D. (1949). "The Infra-Red Spectra of Borine Carbonyl and Tetramethyldiborane". The Journal of Chemical Physics. 17 (2): 218. Bibcode:1949JChPh..17..218C. doi:10.1063/1.1747225.
  7. ↑ Carroll, Benjamin L.; Bartell, Lawrence S. (February 1968). "Molecular structure and internal rotation in tetramethyldiborane. Electron diffraction study". Inorganic Chemistry. 7 (2): 219–222. doi:10.1021/ic50060a009.
  8. ↑ Perras, Frédéric A.; Ewing, William C.; Dellermann, Theresa; Böhnke, Julian; Ullrich, Stefan; Schäfer, Thomas; Braunschweig, Holger; Bryce, David L. (2015). "Spying on the boron–boron triple bond using spin–spin coupling measured from 11B solid-state NMR spectroscopy". Chem. Sci. 6 (6): 3378–3382. doi:10.1039/C5SC00644A. PMC   5657093 . PMID   29142694.
  9. 1 2 Onak, Thomas (1 January 1966). Stone, F. G. A.; West, Robert (eds.). Advances in Organometallic Chemistry. New York, London: Academic Press. p. 284. ISBN   9780080580043 . Retrieved 14 August 2015.
  10. 1 2 Carpenter, J.H.; Jones, W.J.; Jotham, R.W.; Long, L.H. (June 1970). "The Raman spectra of the methyldiboranes—I 1,1 dimethyldiborane and tetramethyldiborane". Spectrochimica Acta Part A: Molecular Spectroscopy. 26 (6): 1199–1214. Bibcode:1970AcSpA..26.1199C. doi:10.1016/0584-8539(70)80027-7.
  11. 1 2 Altschuller, Aubrey P. (4 October 1955). "Calculated Heats of Formation and Combustion of Boron Compounds (Boron, Hydrogen, Carbon, Silicon)" (PDF). NACA Research Memorandum. Cleveland, Ohio: National Advisory Committee for Aeronautics. p. 22. Retrieved 14 August 2015.
  12. ↑ Seely, G. R.; Oliver, J. P.; Ritter, D. M. (December 1959). "Gas-Liquid Chromatographic Analysis of Mixtures Containing Methyldiboranes". Analytical Chemistry. 31 (12): 1993–1995. doi:10.1021/ac60156a032.
  13. ↑ Leach, John B.; Ungermann, Charles B.; Onak, Thomas P. (January 1972). "Proton magnetic resonance studies on methyl and chloro substituted diboranes". Journal of Magnetic Resonance. 6 (1): 74–83. Bibcode:1972JMagR...6...74L. doi:10.1016/0022-2364(72)90088-1.
  14. 1 2 3 4 Brown, Herbert C.; Cole, Thomas E.; Srebnik, Morris; Kim, Kee Won (December 1986). "Hydroboration. 79. Preparation and properties of methylborane and dimethylborane and their characteristics as hydroborating agents. Synthesis of tertiary alcohols containing methyl groups via hydroboration". The Journal of Organic Chemistry. 51 (25): 4925–4930. doi:10.1021/jo00375a031.
  15. ↑ Horn, A; Biener, J; Küppers, J (September 1998). "A dimerization reaction induced by hydrogen atoms: from B(CH3)3 adsorbed on C/Pt(100) to B2H2(CH3)4". Surface Science. 414 (1–2): 290–297. Bibcode:1998SurSc.414..290H. doi:10.1016/S0039-6028(98)00534-2.(subscription required)
  16. ↑ Srebnik, Morris; Cole, Thomas E.; Brown, Herbert C. (August 1990). "Hydroboration. 87. Controlled and sequential hydroboration of simple representative alkenes with methylborane in tetrahydrofuran. An examination of the directive effects in the first and second stages of hydroboration". The Journal of Organic Chemistry. 55 (17): 5051–5058. doi:10.1021/jo00304a017.
  17. 1 2 Bunting, Roger K. (22 Sep 2009). "55 1-Methyldiborane". In Duward F. Shriver (ed.). Inorganic Syntheses, Volume 19. John Wiley and Sons. pp. 237–238. ISBN   978-0471045427.
  18. ↑ Onak, Thomas (1 January 1966). "Carboranes and Organo-Substituted Boron Hydrides". In Stone, F. G. A.; West, Robert (eds.). Advances in Organometallic Chemistry. New York, London: Academic Press. p. 284. ISBN   9780080580043 . Retrieved 19 August 2015.
  19. 1 2 Moews, P. C.; Parry, R. W. (September 1966). "The Reactions between Tetramethyldiborane and Ammonia. The Dimethyldiammineboron(III) Cation, the Dihydridodimethylborate Anion, and Ammonia Dimethylborane". Inorganic Chemistry. 5 (9): 1552–1556. doi:10.1021/ic50043a018.
  20. ↑ Zhao, Qianyi; Li, Jiaxuan; Hamilton, Ewan J.M.; Chen, Xuenian (May 2015). "The continuing story of the diammoniate of diborane". Journal of Organometallic Chemistry. 798: 24–29. doi:10.1016/j.jorganchem.2015.05.027.
  21. 1 2 3 4 Onak, Thomas (2 December 2012). Organoborane Chemistry. Elsevier. pp. 183–184. ISBN   9780323153614 . Retrieved 12 August 2015.
  22. ↑ Lloyd, J. E.; Wade, K. (1964). "325. Reactions between dialkylboranes and methyl cyanide. Ethylideneaminodimethylborane and diethylethylideneaminoborane". Journal of the Chemical Society (Resumed): 1649–1654. doi:10.1039/JR9640001649 . Retrieved 24 July 2015.
  23. ↑ Adams, Roy M. (September 1959). "Organoboron Compounds" (PDF). Metal-Organic Compounds. Advances in Chemistry. Vol. 23. p. 92. doi:10.1021/ba-1959-0023.ch010. ISBN   0-8412-0024-6 . Retrieved 17 August 2015.
  24. 1 2 Mikhailov, B. M. (April 1962). "The Chemistry Of Diborane". Russian Chemical Reviews. 31 (4): 219. Bibcode:1962RuCRv..31..207M. doi:10.1070/RC1962v031n04ABEH001281. S2CID   250909492.
  25. ↑ "tetramethylborate". ChemSpider. Retrieved 19 August 2015.
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