Boron trichloride: Difference between revisions
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{{chembox |
{{chembox |
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| verifiedrevid = 401933692 |
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| verifiedrevid = 437566675 |
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| Name = Boron trichloride |
| Name = Boron trichloride |
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| ImageFileL1 = Boron-trichloride-2D.png |
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| ImageNameL1 = Boron trichloride |
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| ImageFileR1 = Boron-trichloride-3D-vdW.png |
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| ImageNameR1 = Boron trichloride |
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<!-- | ImageSize1 = 150px --> |
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| ImageName1 = Boron trichloride |
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| IUPACName = Boron trichloride |
| IUPACName = Boron trichloride |
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| OtherNames = Boron(III) chloride |
| OtherNames = Boron(III) chloride<br /> |
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Trichloroborane |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = |
| ChemSpiderID = 23480 |
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| InChI = 1/B.3ClH/h;3*1H/q+3;;;/p-3 |
| InChI = 1/B.3ClH/h;3*1H/q+3;;;/p-3 |
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| SMILES = |
| SMILES = ClB(Cl)Cl |
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| InChIKey = PYQQLJUXVKZOPJ-DFZHHIFOAV |
| InChIKey = PYQQLJUXVKZOPJ-DFZHHIFOAV |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = PYQQLJUXVKZOPJ-UHFFFAOYSA-K |
| StdInChIKey = PYQQLJUXVKZOPJ-UHFFFAOYSA-K |
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| CASNo = 10294-34-5 |
| CASNo = 10294-34-5 |
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| |
| CASNo_Ref = {{cascite|correct|CAS}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = K748471RAG |
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| PubChem = 25135 |
| PubChem = 25135 |
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| RTECS = ED1925000 |
| RTECS = ED1925000 |
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| EINECS = 233-658-4 |
| EINECS = 233-658-4 |
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}} |
}} |
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|Section2={{Chembox Properties |
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| Formula = BCl<sub>3</sub> |
| Formula = BCl<sub>3</sub> |
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| MolarMass = 117.17 g/mol |
| MolarMass = 117.17 g/mol |
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| Appearance = Colorless gas,<br />fumes in air |
| Appearance = Colorless gas,<br />fumes in air |
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| Density = 1.326 g/cm<sup>3</sup> |
| Density = 1.326 g/cm<sup>3</sup> |
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| Solubility = |
| Solubility = hydrolysis |
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| SolubleOther = |
| SolubleOther = soluble in [[carbon tetrachloride|CCl<sub>4</sub>]], [[ethanol]] |
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| MeltingPtC = -107.3 |
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| BoilingPtC = 12.6 |
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| BoilingPt = 12.6 °C <ref>Pradyot Patnaik. ''Handbook of Inorganic Chemicals''. McGraw-Hill, 2002, ISBN 0070494398</ref> |
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| BoilingPt_ref = <ref name=EROS/> |
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| RefractIndex = 1.00139 |
| RefractIndex = 1.00139 |
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| MagSus = -59.9·10<sup>−6</sup> cm<sup>3</sup>/mol |
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}} |
}} |
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|Section3={{Chembox Structure |
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| MolShape = [[Trigonal planar molecular geometry|Trigonal planar]] (''D''<sub>3h</sub>) |
| MolShape = [[Trigonal planar molecular geometry|Trigonal planar]] (''D''<sub>3h</sub>) |
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| Dipole = zero |
| Dipole = zero |
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}} |
}} |
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|Section4={{Chembox Thermochemistry |
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| DeltaHf = -427 kJ/mol |
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| Reference = <ref>{{CLP Regulation|index=005-002-00-5|page=341}}</ref> |
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| DeltaGf = -387.2 kJ/mol |
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| EUIndex = 005-002-00-5 |
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| Entropy = 206 J/mol K |
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| ExternalMSDS = {{ICSC-small|0616}} |
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| HeatCapacity = 107 J/mol K |
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| GHSPictograms = {{GHS04|Press. Gas}}{{GHS06|Acute Tox. 2}}{{GHS05|Skin Corr. 1B}} |
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}} |
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| GHSSignalWord = DANGER |
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|Section7={{Chembox Hazards |
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| HPhrases = {{H-phrases|330|300|314}} <ref group="note">Within the European Union, the following additional hazard statement (EUH014) must also be displayed on labelling: Reacts violently with water.</ref> |
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| Hazards_ref = <ref>{{CLP Regulation|index=005-002-00-5|page=341}}</ref> |
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| EUClass = Very toxic ('''T+''')<br/>Corrosive ('''C''') |
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| |
| ExternalSDS = {{ICSC-small|0616}} |
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| GHSPictograms = {{GHS exclamation mark|Press. Gas}}{{GHS skull and crossbones|Acute Tox. 2}}{{GHS corrosion|Skin Corr. 1B}} |
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| SPhrases = {{S1/2}}, {{S9}}, {{S26}}, {{S28}},<br />{{S36/37/39}}, {{S45}} |
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| GHSSignalWord = DANGER |
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| HPhrases = {{H-phrases|330|300|314}}<ref group="note">Within the European Union, the following additional hazard statement (EUH014) must also be displayed on labelling: Reacts violently with water.</ref> |
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| EUPhrases = EUH014 |
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| FlashPt = Non-flammable |
| FlashPt = Non-flammable |
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| MainHazards = May be fatal if swallowed or if inhaled<BR />Causes serious burns to eyes, skin, mouth, lungs, etc.<BR />Contact with water gives HCl |
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| NFPA-H = 4 |
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| NFPA-H = 4 |
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| NFPA-F = 0 |
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| NFPA-R = 2 |
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| NFPA-S = W |
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}} |
}} |
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|Section8={{Chembox Related |
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| OtherAnions = [[Boron trifluoride]]<br />[[Boron tribromide]]<br />[[Boron triiodide]] |
| OtherAnions = [[Boron trifluoride]]<br />[[Boron tribromide]]<br />[[Boron triiodide]] |
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| OtherCations = [[Aluminium |
| OtherCations = [[Aluminium trichloride]]<br />[[Gallium trichloride]] |
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| OtherCompounds = [[Boron trioxide]]<br />[[Carbon tetrachloride]] |
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}} |
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}} |
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'''Boron trichloride''' is |
'''Boron trichloride''' is the [[inorganic compound]] with the formula BCl<sub>3</sub>. This colorless gas is a reagent in [[organic synthesis]]. It is highly reactive towards water. |
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==Production and |
==Production and structure== |
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Boron reacts with [[halogens]] to give the corresponding trihalides. Boron trichloride is, however, produced industrially by direct [[chlorination]] of [[boron oxide]] and [[carbon]] at |
[[Boron]] reacts with [[halogens]] to give the corresponding trihalides. Boron trichloride is, however, produced industrially by direct [[chlorination reaction|chlorination]] of [[boron trioxide|boron oxide]] and [[carbon]] at 501 °C. |
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:B<sub>2</sub>O<sub>3</sub> + 3 C + 3 Cl<sub>2</sub> → 2 BCl<sub>3</sub> + 3 CO |
:B<sub>2</sub>O<sub>3</sub> + 3 C + 3 Cl<sub>2</sub> → 2 BCl<sub>3</sub> + 3 CO |
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The |
The [[carbothermic reaction]] is analogous to the [[Kroll process]] for the conversion of titanium dioxide to titanium tetrachloride. In the laboratory BF<sub>3</sub> reacted with AlCl<sub>3</sub> gives BCl<sub>3</sub> via halogen exchange.<ref name=greenwood>{{Greenwood&Earnshaw}}</ref> BCl<sub>3</sub> is a trigonal planar molecule like the other boron trihalides, and has a bond length of 175pm. |
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A degree of π-bonding has been proposed to explain the short B<nowiki>−</nowiki> Cl distance although there is some debate as to its extent.<ref name = greenwood /> It does not dimerize, although NMR studies of mixtures of boron trihalides shows the presence of mixed halides. The absence of dimerisation contrasts with the tendencies of [[aluminium trichloride|AlCl<sub>3</sub>]] and [[gallium trichloride|GaCl<sub>3</sub>]], which form dimers or polymers with 4 or 6 coordinate metal centres. |
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BCl<sub>3</sub> is a [[Lewis acid]] readily forming [[adduct]]s with tertiary [[amine]]s, [[phosphines]], [[ethers]], [[thioether]]s, and [[halide]] ions.<ref>{{cite journal| author = W. Gerrard and M. F. Lappert| title = Reactions Of Boron Trichloride With Organic Compounds| journal = [[Chemical Reviews]]| year = 1958| volume = 58| issue = 6| pages = 1081–1111| doi = 10.1021/cr50024a003}}</ref> For example, BCl<sub>3</sub>S(CH<sub>3</sub>)<sub>2</sub> (CAS# 5523-19-3) is often employed as a conveniently handled source of BCl<sub>3</sub> because this solid (m.p. 88-90 °C) releases BCl<sub>3</sub>: |
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:(CH<sub>3</sub>)<sub>2</sub>SBCl<sub>3</sub> ⇌ (CH<sub>3</sub>)<sub>2</sub>S + BCl<sub>3</sub> |
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==Reactions== |
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When boron trichloride is passed at low pressure through devices delivering an electric discharge, diboron tetrachloride,<ref>Wartik, T.; Rosenberg, R.; Fox, W. B. "Diboron tetrachloride" Inorganic Syntheses 1967, volume X, pages 118-126.</ref> Cl<sub>2</sub>B-BCl<sub>2</sub>, and tetraboron tetrachloride, formula B<sub>4</sub>Cl<sub>4</sub>, are formed. Colourless diboron tetrachloride (m.p. -93 °C) has a planar molecule in the solid, (similar to [[dinitrogen tetroxide]], but in the gas phase the structure is staggered<ref name = greenwood />. It decomposes at room temperatures to give a series of monochlorides having the general formula (BCl)<sub>''n''</sub>, in which ''n'' may be 8, 9, 10, or 11; the compounds with formulas B<sub>8</sub>Cl<sub>8</sub> and B<sub>9</sub>Cl<sub>9</sub> are known to contain closed cages of boron atoms. |
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BCl<sub>3</sub> hydrolyzes readily to give hydrochloric acid and [[boric acid]]: |
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:BCl<sub>3</sub> + 3 H<sub>2</sub>O → B(OH)<sub>3</sub> + 3 HCl |
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Alcohols behave analogously giving the borate esters, e.g. [[trimethyl borate]]. |
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[[File:NH3-BCl3-adduct-bond-lengthening-2D.png|thumb|250px|left|[[Ammonia]] forms a Lewis [[adduct]] with boron trichloride.]] |
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The mixed [[aryl]] and [[alkyl]] boron chlorides are also of interest. [[Phenyl]]boron dichloride is commercially available. Such species can be prepared by the reaction of BCl<sub>3</sub> with organotin reagents: |
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:2 BCl<sub>3</sub> + R<sub>4</sub>Sn → 2 RBCl<sub>2</sub> + R<sub>2</sub>SnCl<sub>2</sub> |
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As a strong [[Lewis acid]], BCl<sub>3</sub> forms [[adduct]]s with tertiary [[amine]]s, [[phosphines]], [[ethers]], [[thioether]]s, and [[halide]] ions.<ref>{{cite journal | author = Gerrard, W. |author2=Lappert, M. F. | title = Reactions Of Boron Trichloride With Organic Compounds | journal = [[Chemical Reviews]] | year = 1958 | volume = 58 | issue = 6 | pages = 1081–1111 | doi = 10.1021/cr50024a003 }}</ref> Adduct formation is often accompanied by an increase in B-Cl bond length. BCl<sub>3</sub>•S(CH<sub>3</sub>)<sub>2</sub> (CAS# 5523-19-3) is often employed as a conveniently handled source of BCl<sub>3</sub> because this solid (m.p. 88-90 °C) releases BCl<sub>3</sub>: |
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:(CH<sub>3</sub>)<sub>2</sub>S·BCl<sub>3</sub> ⇌ (CH<sub>3</sub>)<sub>2</sub>S + BCl<sub>3</sub> |
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The mixed [[aryl]] and [[alkyl]] boron chlorides are also of known. [[Phenyl]]boron dichloride is commercially available. Such species can be prepared by the [[redistribution reaction]] of BCl<sub>3</sub> with organotin reagents: |
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:2 BCl<sub>3</sub> + R<sub>4</sub>Sn → 2 RBCl<sub>2</sub> + R<sub>2</sub>SnCl<sub>2</sub> |
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===Reduction=== |
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Reduction of BCl<sub>3</sub> to elemental boron is conducted commercially in the laboratory, when boron trichloride can be converted to [[diboron tetrachloride]] by heating with copper metal:<ref>{{cite book |author1=Wartik, T. |author2=Rosenberg, R. |author3=Fox, W. B. | chapter = Diboron Tetrachloride | title = Inorganic Syntheses | year = 1967 | volume = 10 | pages = 118–125 | doi = 10.1002/9780470132418.ch18 |isbn=978-0-470-13241-8 }}</ref> |
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:2 BCl<sub>3</sub> + 2 Cu → B<sub>2</sub>Cl<sub>4</sub> + 2 CuCl |
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B<sub>4</sub>Cl<sub>4</sub> can also be prepared in this way. Colourless diboron tetrachloride (m.p. -93 °C) is a planar molecule in the solid, (similar to [[dinitrogen tetroxide]], but in the gas phase the structure is staggered.<ref name = greenwood /> It decomposes (disproportionates) at room temperatures to give a series of monochlorides having the general formula (BCl)<sub>''n''</sub>, in which ''n'' may be 8, 9, 10, or 11. |
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:n B<sub>2</sub>Cl<sub>4</sub> → B<sub>n</sub>Cl<sub>n</sub> + n BCl<sub>3</sub> |
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The compounds with formulas B<sub>8</sub>Cl<sub>8</sub> and B<sub>9</sub>Cl<sub>9</sub> are known to contain closed cages of boron atoms. |
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==Uses== |
==Uses== |
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Boron trichloride is a starting material for the production of elemental boron. It is also used in the [[refining]] of [[aluminium]], [[magnesium]], |
Boron trichloride is a starting material for the production of elemental boron. It is also used in the [[refining]] of [[aluminium]], [[magnesium]], zinc, and [[copper]] alloys to remove [[nitride]]s, [[carbide]]s, and [[oxides]] from molten metal. It has been used as a soldering flux for alloys of aluminium, [[iron]], [[zinc]], [[tungsten]], and [[monel]]. Aluminium castings can be improved by treating the melt with boron trichloride vapors. In the manufacture of electrical resistors, a uniform and lasting adhesive [[carbon film]] can be put over a [[ceramic]] base using BCl<sub>3</sub>. It has been used in the field of high energy fuels and rocket propellants as a source of boron to raise BTU value. BCl<sub>3</sub> is also used in [[plasma etching]] in [[semiconductor]] manufacturing. This gas etches metal oxides by formation of a volatile BOCl<sub>x</sub> and M<sub>x</sub>O<sub>y</sub>Cl<sub>z</sub> compounds. |
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BCl<sub>3</sub> is used as a [[reagent]] in the synthesis of organic compounds. Like the corresponding bromide, it cleaves C-O bonds in [[ether]]s.<ref name=EROS>{{cite encyclopedia |author1=Yamamoto, Y.|author2-link=Norio Miyaura |author2=Miyaura, N. | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | editor = Paquette, L. | year = 2004 | publisher = J. Wiley & Sons | location = New York | doi = 10.1002/047084289X.rb245.pub2 | isbn = 0-471-93623-5|entry=Boron Trichloride }}</ref><ref>{{cite journal|title=Trichloroboron-promoted Deprotection of Phenolic Benzyl Ether Using Pentamethylbenzene as a Non Lewis-Basic Cation Scavenger |author=Shun Okaya |author2=Keiichiro Okuyama |author3=Kentaro Okano |author4=Hidetoshi Tokuyama|journal=Org. Synth.|year=2016|volume=93|pages=63–74|doi=10.15227/orgsyn.093.0063|doi-access=free}}</ref> |
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BCl<sub>3</sub> is used as a [[reagent]] in the synthesis of organic compounds. Like the corresponding bromide, it cleaves C-O bonds in [[ether]]s.<ref> |
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Yamamoto, Y.; Miyaura, N. "Boron Trichloride" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.</ref> |
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==Safety== |
==Safety== |
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BCl<sub>3</sub> is an aggressive reagent that |
BCl<sub>3</sub> is an aggressive reagent that can form [[hydrogen chloride]] upon exposure to moisture or [[Alcohol (chemistry)|alcohol]]s. The [[dimethyl sulfide]] adduct (BCl<sub>3</sub>SMe<sub>2</sub>), which is a solid, is much safer to use,<ref>{{Cite journal | doi = 10.1016/0040-4039(80)80164-X | title = Boron trihalide-methyl sulfide complexes as convenient reagents for dealkylation of aryl ethers | year = 1980 | last1 = Williard | first1 = Paul G. | last2 = Fryhle | first2 = Craig B. | journal = Tetrahedron Letters | volume = 21 | issue = 39 | page = 3731}}</ref> when possible, but H<sub>2</sub>O will destroy the BCl<sub>3</sub> portion while leaving dimethyl sulfide in solution. |
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==See also== |
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*[[List of highly toxic gases]] |
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==References== |
==References== |
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{{Reflist}} |
{{Reflist}} |
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==Notes== |
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<references group="note"/> |
<references group="note"/> |
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==See also== |
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*[[List of highly toxic gases]] |
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== Further reading == |
== Further reading == |
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{{refbegin}} |
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<div class="references-small"> |
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* {{cite journal | author = Martin, D. R. | title = Coordination Compounds of Boron Trichloride. I. - A Review | journal = [[Chemical Reviews]] | year = 1944 | volume = 34 | issue = 3 | pages = 461–473 | doi = 10.1021/cr60109a005}} |
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*{{cite journal |
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* {{cite journal |author1=Kabalka, G. W. |author2=Wu, Z. Z. |author3=Ju, Y. H. | title = The Use of Organoboron Chlorides and Bromides in Organic Synthesis | journal = Journal of Organometallic Chemistry | year = 2003 | volume = 680 | issue = 1–2 | pages = 12–22 | doi = 10.1016/S0022-328X(03)00209-2 }} |
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| author = D. R. Martin |
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{{refend}} |
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| title = Coordination compounds of boron trichloride. I - A review |
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| journal = [[Chemical Reviews]] |
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| year = 1944 |
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| volume = 34 |
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| issue = 3 |
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| pages = 461–473 |
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| doi = 10.1021/cr60109a005}} |
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* {{cite journal |
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| author = Kabalka GW, Wu ZZ, Ju YH |
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| title = The use of organoboron chlorides and bromides in organic synthesis |
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| journal = Journal of Organometallic Chemistry |
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| year = 2003 |
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| volume = 680 |
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| issue = 1-2 |
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| pages = 12–22 |
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| doi = 10.1016/S0022-328X(03)00209-2}}<references /></div> |
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==External links== |
==External links== |
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{{Boron compounds}} |
{{Boron compounds}} |
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{{Chlorides}} |
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{{Authority control}} |
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[[Category:Boron compounds]] |
[[Category:Boron compounds]] |
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[[Category:Chlorides]] |
[[Category:Chlorides]] |
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[[Category:Nonmetal halides]] |
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[[Category:Boron halides]] |
[[Category:Boron halides]] |
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[[cs:Chlorid boritý]] |
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[[de:Bortrichlorid]] |
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[[fr:Trichlorure de bore]] |
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[[nl:Boortrichloride]] |
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[[pl:Chlorek boru]] |
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[[pt:Tricloreto de boro]] |
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[[ru:Трихлорид бора]] |
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[[sv:Bortriklorid]] |
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[[zh:三氯化硼]] |