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| verifiedrevid = 290610475 |
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| Name = Molybdenum(V) chloride |
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| verifiedrevid = 428807101 |
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| ImageFile = |
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| Name = Molybdenum(V) chloride |
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| ImageSize = |
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| ImageFile = Mo2Cl10Sttructure.png |
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| ImageName = Molybdenum(V) chloride |
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| ImageSize = |
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| IUPACName = Molybdenum(V) chloride<br/>Molybdenum pentachloride |
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| ImageName = Molybdenum(V) chloride |
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| OtherNames = |
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| ImageFile1 = Molybdenum(V)-chloride-from-xtal-3D-balls.png |
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| Section1 = {{Chembox Identifiers |
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| ImageSize1 = |
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| CASNo = 10241-05-1 |
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| ImageName1 = Ball-and-stick model of the Mo2Cl10 molecule in the crystal structure |
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| CASNo_Ref = {{cascite}} |
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| ImageFile2 = Molybdenum pentachloride.png |
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| RTECS = QA4690000 |
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| ImageCaption2 = Partially oxidized MoCl<sub>5</sub> |
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}} |
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| IUPACName = Molybdenum(V) chloride<br />Molybdenum pentachloride |
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| Section2 = {{Chembox Properties |
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| OtherNames = |
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| Formula = Cl<sub>10</sub>Mo<sub>2</sub> |
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|Section1={{Chembox Identifiers |
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| MolarMass = 273.21 g/mol |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| Appearance = dark-green solid <br> ] <br> ] |
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| CASNo = 10241-05-1 |
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| Density = 2.928 g/cm<sup>3</sup> |
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| CASNo1_Comment = MoCl<sub>5</sub> |
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| Solubility = hydrolyzes |
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| UNII_Ref = {{fdacite|changed|FDA}} |
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| SolubleOther = soluble in dry ], dry ], ] |
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| UNII = BB0UFP2VO5 |
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| MeltingPt = 194 °C |
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| RTECS = QA4690000 |
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| BoilingPt = 268 °C |
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| PubChem = 61497 |
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}} |
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| EINECS = 233-575-3 |
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| Section3 = {{Chembox Structure |
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| SMILES1 = Cl(Cl)(Cl)(Cl)Cl |
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| Coordination = edge-shared bioctahedron |
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| SMILES2 = Cl1(Cl)(Cl)(Cl)(Cl)Cl1(Cl)(Cl)(Cl)Cl |
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| CrystalStruct = monoclinic |
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| InChI1 = 1S/5ClH.Mo/h5*1H;/q;;;;;+5/p-5 |
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| Dipole = |
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| InChI2 = 1S/10ClH.2Mo/h10*1H;;/q;;;;;;;;;;2*+4/p-8 |
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| Section7 = {{Chembox Hazards |
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|Section2={{Chembox Properties |
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| ExternalMSDS = |
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| Formula = {{chem2|Mo2Cl10}} |
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| EUIndex = Not listed |
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| MolarMass = 273.21 g/mol ({{chem2|MoCl5}}) |
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| MainHazards = oxidizer, hydrolyzes to release HCl |
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| Appearance = dark-green solid <br> ] <br> ] |
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| Density = 2.928 g/cm<sup>3</sup> |
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| SPhrases = |
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| Solubility = hydrolyzes |
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| FlashPt = Non-flammable |
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| SolubleOther = soluble in dry ], dry ], ] |
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| MeltingPtC = 194 |
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| BoilingPtC = 268 |
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| OtherAnions = ]<br/>]<br/>] |
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| OtherCations = ]<br/>] |
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|Section3={{Chembox Structure |
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| OtherFunctn = ]<br/>]<br/>] |
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| Coordination = edge-shared bioctahedron |
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| Function = molybdenum chlorides |
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| CrystalStruct = monoclinic |
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| Dipole = |
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|Section7={{Chembox Hazards |
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| ExternalSDS = |
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| MainHazards = oxidizer, hydrolyzes to release HCl |
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| FlashPt = Non-flammable |
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}} |
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|Section8={{Chembox Related |
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| OtherAnions = {{ubl|]|]|]}} |
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| OtherCations = {{ubl|]|]}} |
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| OtherFunction = {{ubl|]|]|]}} |
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| OtherFunction_label = molybdenum chlorides |
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'''Molybdenum(V) chloride''' is the ] with the formula <sub>2</sub>. This dark volatile solid is an important starting reagent in the preparation of molybdenum compounds. In the solid state molybdenum pentachloride exists as a dimer with the formula Mo<sub>2</sub>Cl<sub>10</sub>, with a structure similar to that of the corresponding pentachlorides of W, Nb and Ta. In the gas phase, it is a monomeric pentahalide. It is paramagnetic, with one unpaired electron per Mo center, reflecting the fact that the formal oxidation state is 5+, leaving one valence electron. |
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'''Molybdenum(V) chloride''' is the ] with the ] {{chem2|MoCl5}}. This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents. |
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==Structure== |
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Usually called molybdenum pentachloride, it is in fact partly a ] with the ] {{chem2|Mo2Cl10}}.<ref>{{cite book|last1=Holleman |first1=A. F.|last2= Wiberg|first2= E. |title=Inorganic Chemistry |publisher=Academic Press|location=San Diego, CA|date= 2001 |isbn=0-12-352651-5}}</ref> In the dimer, each molybdenum has local octahedral symmetry and two chlorides ] between the molybdenum centers.<ref>{{cite journal|first1=J. |last1=Beck |first2=F. |last2=Wolf |title=Three New Polymorphic Forms of Molybdenum Pentachloride|journal= Acta Crystallogr. |date=1997 |volume=B53 |issue=6 |pages=895–903|doi=10.1107/S0108768197008331|s2cid=95489209 |doi-access= }}</ref> A similar structure is also found for the pentachlorides of W, Nb and Ta.<ref>{{cite book|last=Wells|first= A. E. |date=1984 |title=Structural Inorganic Chemistry |edition=5th |location=Oxford |publisher=Clarendon Press}}</ref> In the gas phase and partly in solution, the ]s partially dissociate to give a monomeric {{chem2|MoCl5}}.<ref>{{cite journal|last1=Brunvoll |first1=J. |last2=Ischenko |first2=A. A. |last3=Spiridonov |first3=V. P. |last4=Strand |first4=T. G. |title=Composition and Molecular Structure of Gaseous Molybdenum Pentachloride by Electron Diffraction|journal=Acta Chem. Scand. |date=1984 |volume=A38 |pages=115–120|doi=10.3891/acta.chem.scand.38a-0115|doi-access=free }}</ref> The monomer is paramagnetic, with one unpaired electron per Mo center, reflecting the fact that the formal oxidation state is +5, leaving one valence electron on the metal center. |
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==Preparation and properties== |
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==Preparation and properties== |
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{{chem2|MoCl5}} is prepared by chlorination of Mo metal but also chlorination of {{chem2|MoO3}}. The unstable hexachloride {{chem2|MoCl6}} is not produced in this way.<ref>{{ cite journal | first1 = Farhad | last1 = Tamadon | first2 = Konrad | last2 = Seppelt | title = The Elusive Halides VCl<sub>5</sub>, MoCl<sub>6</sub>, and ReCl<sub>6</sub> | journal = ] | year = 2013 | volume = 52 | issue = 2 | pages = 767–769 | doi = 10.1002/anie.201207552 | pmid = 23172658 }}</ref> |
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MoCl<sub>5</sub> is prepared by chlorination of Mo metal but also chlorination of MoO<sub>3</sub>. Notice that MoCl<sub>6</sub> ''cannot'' be prepared under normal conditions. In contrast, the heavier analogues ] is well known.<ref>Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.</ref> |
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MoCl<sub>5</sub> is a strong oxidant, as indicated by its non-reactivity toward Cl<sub>2</sub>. It is easily reduced by even MeCN to afford the adduct MoCl<sub>4</sub>(MeCN)<sub>2</sub>, which in turn reacts with ] to give MoCl<sub>4</sub>(THF)<sub>2</sub>, a versatile reagent in the chemistry of molybdenum.<ref>Dilworth, J. R.; Richards, R. L. "The Synthesis of Molybdenum and Tungsten Dinitrogen Compounds" Inorganic Syntheses, 1990, volume 28, pages 33-45. ISBN 0-471-52619-3.</ref> MoCl<sub>5</sub> is reduced by HBr to form MoBr<sub>4</sub>. The reaction is conducted in ethylbromide at -50 C: |
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{{chem2|MoCl5}} is reduced by acetonitrile to afford an orange ], {{chem2|MoCl4(CH3CN)2}}. This complex in turn reacts with ] to give {{chem2|MoCl4(THF)2}}, a precursor to other molybdenum-containing complexes.<ref>{{cite book| series = Inorganic Syntheses | volume = 28 | chapter = The Synthesis of Molybdenum and Tungsten Dinitrogen Complexes | year = 1990 |doi=10.1002/9780470132593.ch7| last1 = Dilworth | first1 = Jonathan R. | last2 = Richards | first2 = Raymond L. | title = Inorganic Syntheses | pages = 33–43 | isbn = 9780470132593 }}</ref> |
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:: 2 MoCl<sub>5</sub> + 10 HBr → 2 MoBr<sub>4</sub> + 10 HCl + Br<sub>2</sub> |
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MoBr<sub>4</sub> reacts with THF to give the Mo(III) species mer-MoBr<sub>3</sub>(THF)<sub>3</sub>.<ref>Calderazzo, F.; Maichle-Mössmer, C.; Pampaloni, G.; Strähle, J. "Low-temperature Syntheses of Vanadium(III) and Molybdenum(IV) Bromides by Halide Exchange", Journal of the Chemical Society, Dalton Transactions, 1993, pages 655-8.{{DOI|10.1039/DT9930000655}}</ref> |
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] is prepared by treatment of {{chem2|MoCl5}} with ]: |
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MoCl<sub>5</sub> is a good Lewis acid toward non-oxidizable ligands. It forms an adduct with chloride to form <sup>-</sup>. In ], the compound finds occasional use in chlorinations and deoxygenation reactions.<ref>T. Kauffmann, S. Torii, T. Inokuchi “Molybdenum(V) Chloride” in Encyclopedia of Reagents for Organic Synthesis 2004, J. Wiley & Sons, New York. {{DOI|10.1002/047084289}}.</ref> |
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:{{chem2|2 MoCl5 + 10 HBr → 2 MoBr4 + 10 HCl + Br2}} |
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The reaction proceeds via the unstable molybdenum(V) bromide, which releases bromine at room temperature.<ref>{{cite journal|doi=10.1039/DT9930000655|title=Low-Temperature Syntheses of Vanadium(III) and Molybdenum(IV) Bromides by Halide Exchange|journal= J. Chem. Soc., Dalton Trans.|issue=5|pages=655–658|year=1993|last1=Calderazzo|first1=Fausto|last2=Maichle-Mössmer|first2=Cäcilie|last3=Pampaloni|first3=Guido|last4=Strähle|first4=Joachim}}</ref> |
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{{chem2|MoCl5}} is a good ] toward non-oxidizable ligands. It forms an adduct with chloride to form {{chem2|−}}. In ], the compound finds occasional use in ], ], and oxidative coupling reactions.<ref>{{cite encyclopedia|first1=T.|last1= Kauffmann|first2= S.|last2= Torii|first3= T.|last3= Inokuchi |title=Molybdenum(V) Chloride |encyclopedia=Encyclopedia of Reagents for Organic Synthesis |date=2004 |publisher=J. Wiley & Sons |location=New York, NY|doi=10.1002/047084289X|isbn= 9780471936237|hdl=10261/236866|hdl-access=free}}</ref> |
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==Reactions== |
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{{chem2|MoCl5}} is reduced by ]:<ref>{{cite book |volume = 28 | title = The Synthesis of Molybdenum and Tungsten Dinitrogen Complexes | year = 1990 |doi=10.1002/9780470132593.ch7| last1 = Dilworth | first1 = Jonathan R. | last2 = Richards | first2 = Raymond L. | series = Inorganic Syntheses | pages = 33–43| isbn = 9780470132593 }}</ref> |
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:{{chem2|2 MoCl5 + 5 CH3CN → 2 MoCl4(CH3CN)2 + HCl + ClCH2CN}} |
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Although it polymerizes ], {{chem2|MoCl5}} is stable in ]. Reduction of such solutions with tin gives {{chem2|MoCl4((CH3CH2)2O)2}} and {{chem2|MoCl3((CH3CH2)2O)3}}, depending on conditions.<ref>{{cite book |doi=10.1002/9781118744994.ch03|chapter=Ether Complexes of Molybdenum(III) and Molybdenum(IV) chlorides |series=Inorganic Syntheses| volume =36 |year=2014 |last1=Maria |first1=Sébastien |last2=Poli |first2=Rinaldo |title=Inorganic Syntheses: Volume 36 |pages=15–18|isbn=9781118744994 |url=https://hal.archives-ouvertes.fr/hal-02042499/file/332-10.1002-9781118744994.ch03-Accepted.pdf }}</ref> |
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==Safety considerations== |
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==Safety considerations== |
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MoCl<sub>5</sub> is an aggressive oxidant and readily hydrolyzes to release HCl. |
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{{chem2|MoCl5}} is an aggressive oxidant and readily hydrolyzes to release HCl. |
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==See also== |
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* ] |
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* ] |
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* ] |
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* ] |
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==References== |
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==References== |
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<references/> |
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<references /> |
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{{Molybdenum compounds}} |
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{{Molybdenum compounds}} |
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{{Chlorides}} |
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