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{{chembox |
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| verifiedrevid = 344157348 |
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| verifiedrevid = 428892782 |
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| Name = Niobium(IV) chloride |
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| Name = Niobium(IV) chloride |
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| ImageFile = NbCl4.png |
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| ImageFile = NbCl4.png |
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<!-- | ImageSize = 150px --> |
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| ImageFile1 = Niobium-tetrachloride-chain-from-xtal-1977-3D-balls.png |
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| ImageFile1 = Niobium-tetrachloride-chain-from-xtal-1977-3D-balls.png |
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| ImageFile2 = Niobium-tetrachloride-xtal-1977-A-3D-balls.png |
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| ImageFile2 = Niobium-tetrachloride-xtal-1977-A-3D-balls.png |
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| IUPACName = Niobium(IV) chloride |
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| IUPACName = Niobium(IV) chloride |
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| OtherNames = Niobium tetrachloride<br/>Niobium chloride |
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| OtherNames = Niobium tetrachloride<br/>Niobium chloride |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo = 13569-70-5 |
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| CASNo = 13569-70-5 |
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| CASNo_Ref = |
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| CASNo_Ref = {{cascite|correct|??}} |
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| EINECS = |
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| EINECS = |
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| RTECS = |
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| RTECS = |
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| PubChem = 83583 |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = NbCl<sub>4</sub> |
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| Formula = NbCl<sub>4</sub> |
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| MolarMass = 234.718 g/mol |
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| MolarMass = 234.718 g/mol |
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| Appearance = Violet-Black Crystals |
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| Appearance = Violet-Black Crystals |
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| Density = 3.2 g/cm<sup>3</sup> |
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| Density = 3.2 g/cm<sup>3</sup> |
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| Solubility = Reacts |
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| Solubility = Reacts |
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| MeltingPt = Dec. 800 °C |
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| MeltingPt = Dec. 800 °C |
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| BoilingPt = Subl. 275 °C/10<sup>-4</sup> mmHg |
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| BoilingPt = Subl. 275 °C/10<sup>−4</sup> mmHg |
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| Section8 = {{Chembox Related |
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|Section8={{Chembox Related |
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| OtherAnions = ]<br/>] |
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| OtherAnions = ]<br/>] |
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| OtherCations = ]<br/>] |
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| OtherCations = ]<br/>] |
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| OtherFunctn = ]<br/>] |
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| OtherFunction = ]<br/>] |
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| Function = niobium chlorides <ref name = CRC>CRC, Handbook of Chemistry and Physics, 89th Ed., 2008/09, editor D. Lide, Cleveland, OH: CRC Press, p. 4-36. </ref> |
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| OtherFunction_label = niobium chlorides <ref name = CRC>CRC, Handbook of Chemistry and Physics, 89th Ed., 2008/09, editor D. Lide, Cleveland, OH: CRC Press, p. 4-36.</ref> |
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==Structure and properties== |
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==Structure and properties== |
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In the solid state, niobium(IV) chloride exists as chains of edge-sharing ] with alternating Nb-Nb distances of lengths 302.9 and 379.4 pm. The shorter distances correspond to Nb-Nb bonds, forming a ] resulting in the compound’s ]. This metal bond forms as ] forms ] in its +4 ], resulting in lone electrons. Other ] with the formula NbCl<sub>4</sub>L<sub>2</sub>, such as tetrachlorobis(tetrahydrofuran) niobium, only form ] resulting in one unpaired electron in the d<sub>xy</sub> orbital, making the compounds ].<ref name = Cotton>{{cite journal | author = Cotton, F. A..; Lu, J. | title = EPR and Crystallographic Studies of Some Reaction Products of VCl<sub>4</sub>, NbCl<sub>4</sub>, and TaCl<sub>4</sub> with Trialkyl- and Triarylphosphines | journal =] | doi = 10.1021/ic00114a023 | year = 1995 | volume = 34 | pages = 2639}}</ref> |
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In the solid state, niobium(IV) chloride exists as chains of edge-sharing ] with alternating Nb-Nb distances of lengths 302.9 and 379.4 pm. The shorter distances correspond to Nb-Nb bonds, which result in the compound's ]. Its structure is very similar to that of ]. |
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Other ] with the formula NbCl<sub>4</sub>L<sub>2</sub>, such as tetrachlorobis(tetrahydrofuran) niobium, only form ] resulting in one unpaired electron in the d<sub>''xy''</sub> orbital, making the compounds ].<ref name = Cotton>{{cite journal |author1=Cotton, F. A.. |author2=Lu, J. | title = EPR and Crystallographic Studies of Some Reaction Products of VCl<sub>4</sub>, NbCl<sub>4</sub>, and TaCl<sub>4</sub> with Trialkyl- and Triarylphosphines | journal =] | doi = 10.1021/ic00114a023 | year = 1995 | volume = 34 | pages = 2639 | issue = 10}}</ref> |
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Niobium chloride rapidly oxidizes and hydrolyzes in air to form ]. |
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Niobium chloride rapidly oxidizes and hydrolyzes in air to form ]. |
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==Preparation== |
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==Preparation== |
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Niobium(IV) chloride is typically produced by allowing elemental ] and ] crystals to react over several days in a temperature gradient, with the metal around 400 °C and the salt around 250 °C.<ref name = McCarley>{{cite journal | author = McCarley, Robert E.; Torp, Bruce A. | title = The preparation and properties of niobium(IV) compounds. I. Some niobium(IV) halides and their pyridine adducts | journal = ] | doi = 10.1021/ic50007a029 | year = 1963 | volume = 2 | pages = 540}}</ref> |
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Niobium(IV) chloride is typically produced by allowing elemental ] and ] crystals to react over several days in a temperature gradient, with the metal around 400 °C and the salt around 250 °C.<ref name = McCarley>{{cite journal |author1=McCarley, Robert E. |author2=Torp, Bruce A. | title = The preparation and properties of niobium(IV) compounds. I. Some niobium(IV) halides and their pyridine adducts | journal = ] | doi = 10.1021/ic50007a029 | year = 1963 | volume = 2 | pages = 540 | issue = 3}}</ref> |
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:4 NbCl<sub>5</sub> + Nb → 5 NbCl<sub>4</sub> |
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:4 NbCl<sub>5</sub> + Nb → 5 NbCl<sub>4</sub> |
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A similar technique is also used in the synthesis of ] and ]. ] exists as well and may be synthesized by thermal decomposition of ]. |
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A similar technique is also used in the synthesis of ] and ]. ] exists as well and may be synthesized by thermal decomposition of ]. |
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At 400 °C NbCl<sub>4</sub> disproportiates: |
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At 400 °C NbCl<sub>4</sub> disproportiates: |
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:2 NbCl<sub>4</sub> → NbCl<sub>3</sub> + NbCl<sub>5</sub> |
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:2 NbCl<sub>4</sub> → NbCl<sub>3</sub> + NbCl<sub>5</sub> |
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==Reactions== |
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==Reactions== |
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The disproportiation of niobium(IV) chloride can be used to make tetrachlorobis(tetrahydrofuran) niobium, a useful ] in Nb<sup>IV</sup> chemistry due to the lability of the attached ] ].<ref name = Hubert>Hubert-Pfalzgraf, L.G. Niobium & Tantalum: Inorganic & Coordination Chemistry. 2006: John Wiley & Sons, Ltd. </ref>This compound can be synthesized by first reacting ] with ] in ] followed by addition of ] to the resultant solid by the following reaction.<ref name = Manzer>{{cite journal | author = Manzer, L.E. | journal = ] | doi = 10.1021/ic50169a004 | title = Preparation of the paramagnetic alkyls bis(cyclopentadienyl)dimethylniobium and bis(methylcyclopentadienyl)dimethyltantalum and some six- and eight-coordinate phosphine derivatives of niobium(IV) | year = 1977 | volume = 16 | pages = 525}}</ref> |
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The disproportiation of niobium(IV) chloride can be used to make tetrachlorobis(tetrahydrofuran) niobium, a useful ] in Nb<sup>IV</sup> chemistry due to the lability of the attached ] ].<ref name = Hubert>Hubert-Pfalzgraf, L.G. Niobium & Tantalum: Inorganic & Coordination Chemistry. 2006: John Wiley & Sons, Ltd.</ref> This compound can be synthesized by first reacting ] with ] in ] followed by addition of ] to the resultant solid by the following reaction.<ref name = Manzer>{{cite journal | author = Manzer, L.E. | journal = ] | doi = 10.1021/ic50169a004 | title = Preparation of the paramagnetic alkyls bis(cyclopentadienyl)dimethylniobium and bis(methylcyclopentadienyl)dimethyltantalum and some six- and eight-coordinate phosphine derivatives of niobium(IV) | year = 1977 | volume = 16 | pages = 525–528 | issue = 3}}</ref> |
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: 3 NbCl<sub>5</sub> + Al + 3 CH<sub>3</sub>CN → 3 NbCl<sub>4</sub>(NCCH<sub>3</sub>)<sub>3</sub> + AlCl<sub>3</sub> |
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| ⚫ |
: 3 NbCl<sub>4</sub>(NCCH<sub>3</sub>)<sub>3</sub> + AlCl<sub>3</sub> + 3 C<sub>4</sub>H<sub>8</sub>O → 3 NbCl<sub>4</sub>(thf)<sub>2</sub> + 9 MeCN + AlCl<sub>3</sub>(thf) |
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: 3 NbCl<sub>5</sub> + Al + 3 CH<sub>3</sub>CN → 3 NbCl<sub>4</sub>(NCCH<sub>3</sub>)<sub>3</sub> + AlCl<sub>3</sub> |
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Niobium chloride has been used in the syntheses of ] which can be used as ] or ] inhibitors. |
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: 3 NbCl<sub>4</sub>(NCCH<sub>3</sub>)<sub>3</sub> + AlCl<sub>3</sub> + 3 C<sub>4</sub>H<sub>8</sub>O → 3 NbCl<sub>4</sub>(thf)<sub>2</sub> + 9 MeCN + AlCl<sub>3</sub>(thf) |
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==References== |
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==References== |
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{{Niobium compounds}} |
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{{Niobium compounds}} |
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{{Chlorides}} |
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