| Revision as of 20:14, 12 November 2010 editRjwilmsi (talk | contribs)Extended confirmed users, Pending changes reviewers, Rollbackers932,125 editsm Dupe ref fixes (explanation), Kubas1979 using AWB (7383)← Previous edit |
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{{Chembox |
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{{Chembox |
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| verifiedrevid = 396377376 |
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| ImageFile = Tetrakis(acetonitrile)copper(I) hexafluorophosphate.png |
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| ImageFile = Tetrakis(acetonitrile)copper(I) hexafluorophosphate.png |
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| ImageSize = 200px |
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| ImageSize = 260 |
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| IUPACName = Tetrakis(acetonitile)copper(I) hexafluorophosphate |
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| ImageAlt = Structural formulas of the tetrakis(acetonitrile)copper(I) cation and the hexafluorophosphate anion |
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| ImageFile1 = Tetrakis(acetonitrile)copper(I) hexafluorophosphate 3D spacefill.png |
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| OtherNames = |
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| ImageSize1 = 220 |
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| Section1 = {{Chembox Identifiers |
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| ImageAlt1 = Space-filling models of the component ions of tetrakis(acetonitrile)copper(I) hexafluorophosphate |
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| IUPACName = Tetrakis(acetonitrile)copper(I) hexafluorophosphate |
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|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 64443-05-6 |
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| CASNo = 64443-05-6 |
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| PubChem = |
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| PubChem = 11068737 |
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}} |
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| SMILES = }} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = PF<sub>6</sub> |
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| Formula = PF<sub>6</sub> |
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| MolarMass = 372.7198 g/mol |
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| MolarMass = 372.7198 g/mol |
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| Appearance = White powder |
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| Appearance = White powder |
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| Density = |
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| MeltingPtC = 160 |
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| MeltingPtC = 160 |
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| Section3 = {{Chembox Hazards |
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'''Tetrakis(acetonitrile)copper(I) hexafluorophosphate''' is a copper(I) coordination complex with the formula PF<sub>6</sub>. |
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'''Tetrakis(acetonitrile)copper(I) hexafluorophosphate''' is a salt with the formula PF<sub>6</sub>. It is a colourless solid that is used in the synthesis of other copper complexes. The ] <sup>+</sup> is a well-known example of a ].<ref name=Rach>Silvana F. Rach, Fritz E. Kühn "Nitrile Ligated Transition Metal Complexes with Weakly Coordinating Counteranions and Their Catalytic Applications" Chem. Rev., 2009, volume 109, pp 2061–2080. {{doi|10.1021/cr800270h}}</ref> |
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==Properties== |
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==Structure== |
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As confirmed by ], the copper(I) ion is coordinated to four almost linear acetonitrile ligands in a nearly ideal tetrahedral geometry.<ref>{{cite journal | author = Kierkegaard C.P. |author2=Norrestam R. | year = 1975 |title = Copper(I) tetraacetonitrile perchlorate | journal = ] | volume = 31|issue=1 | pages = 314–317 | doi = 10.1107/S0567740875002634|bibcode=1975AcCrB..31..314C }}</ref><ref>{{cite journal|doi=10.1107/S0108270194012527|title=Tetrakis(acetonitrile-N)copper(I) Hexafluorophosphate(V) Acetonitrile Solvate|year=1995|last1=Black|first1=J. R.|last2=Levason|first2=W.|last3=Webster|first3=M.|journal=Acta Crystallographica Section C Crystal Structure Communications|volume=51|issue=4|pages=623–625|bibcode=1995AcCrC..51..623B }}</ref> Similar complexes with other anions including the perchlorate, ], and ] are known.<ref name=Rach/> |
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At room temperature the compound is a free-flowing, white microcrystalline powder. However due to its slightly hygroscopic nature, the compound may oxidize and darken upon exposure to air.<ref name="Kubas1979">{{cite journal |
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| author = Kubas, G.J. |
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| coauthors = |
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| year = 1979 |
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| title = Tetrakis(acetonitirile)copper(I) Hexaflurorophosphate |
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| journal = ] |
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| volume = 19 |
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| issue = |
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| pages = 90–91 |
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| doi = 10.1002/9780470132593.ch15 |
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| last2 = Monzyk |
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| first2 = B. |
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| last3 = Crumblis |
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| first3 = A. L. |
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}}</ref> Additionally, the <sup>+</sup> cation is much more stabilized by large anions such as PF<sub>6</sub><sup>-</sup> . The compound is moderately soluble in most polar solvents. |
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According to X-ray crystallographic studies, the copper(I) ion is coordinated to four almost linear acetonitrile ligands in a nearly ideal tetrahedral geometry.<ref name="Kierkegaard1975">{{cite journal |
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| author = Kierkegaard C.P. |
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| coauthors = Norrestam R. |
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| year = 1975 |
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| title = Copper(I) tetraacetonitrile perchlorate |
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| journal = ] |
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| volume = B31 |
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| issue = |
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| pages = 314–317 |
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| doi = 10.1107/S0567740875002634 |
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}}</ref> The acetonitrile ligands protect the Cu<sup>+</sup> ion from oxidation to Cu<sup>2+</sup>. However, acetonitrile is not bound very strongly to the copper ion, and upon their removal Cu<sup>+</sup> will readily oxidize to Cu<sup>2+</sup>. |
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==Synthesis== |
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==Synthesis== |
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The cation was first isolated in 1923 with a nitrate anion as a byproduct of the reduction of silver nitrate with copper powder in acetonitrile.<ref name="Morgan1923">{{cite journal |
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The cation was first reported in 1923 with a nitrate anion as a byproduct of the reduction of ] with a suspension of copper powder in acetonitrile.<ref>{{cite journal| author = Morgan, H.H. | year = 1923 | title = Preparation and Stability of Cuprous Nitrate and Other Cuprous Salts in the Presence of Nitriles | journal = ] | volume = 19| pages = 2901 | doi = 10.1039/CT9232302901 | last2 = Sand | first2 = Henry Julics Salomon}}</ref> PF<sub>6</sub> is generally produced by the addition of HPF<sub>6</sub> to a suspension of ] in acetonitrile:<ref name="Kubas1979"/> |
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| author = Morgan, H.H. |
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| coauthors = |
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| year = 1923 |
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| title = Preparation and Stability of Cuprous Nitrate and Other Cuprous Salts in the presence of Nitriles |
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| journal = ] |
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| volume = 19 |
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| issue = |
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| pages = 2901 |
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| doi = 10.1039/CT9232302891 |
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| last2 = Sand |
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| first2 = Henry Julics Salomon |
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}}</ref> PF<sub>6</sub> is generally produced by the addition of HPF<sub>6</sub> to a suspension of copper(I) oxide in acetonitrile.<ref name="Kubas1979"/> The reaction is highly exothermic, and may bring the solution to a boil. Upon crystallization, the resulting microcrystals should be white, though a blue tinge is common, indicating the presence of a Cu<sup>2+</sup> species. |
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:Cu<sub>2</sub>O + 2 HPF<sub>6</sub> + 8 CH<sub>3</sub>CN → 2 PF<sub>6</sub> + H<sub>2</sub>O |
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:Cu<sub>2</sub>O + 2 HPF<sub>6</sub> + 8 CH<sub>3</sub>CN → 2 PF<sub>6</sub> + H<sub>2</sub>O |
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The reaction is highly exothermic, and may bring the solution to a boil. Upon crystallization, the resulting microcrystals should be white, though a blue tinge is common, indicating the presence of Cu<sup>2+</sup> impurities.<ref name="Kubas1979">{{cite book | author = Kubas, G.J. | year = 1990 | title = Tetrakis(acetonitirile)copper(I) Hexaflurorophosphate | series = ] | volume = 28 | pages = 68–69 | doi = 10.1002/9780470132593.ch15}}</ref> |
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==Reactions and applications== |
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==Applications== |
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The acetonitrile ligands protect the Cu<sup>+</sup> ion from oxidation to Cu<sup>2+</sup>, but are rather poorly bound: with other counterions, the complex forms di-<ref name=Rach/> and tri-acetonitrilo<ref>{{cite journal |doi=10.1039/C8DT03723J|title=Highly soluble Cu(i)-acetonitrile salts as building blocks for novel phosphorus-rich organometallic-inorganic compounds|year=2018|last1=Elsayed Moussa|first1=Mehdi|last2=Piesch|first2=Martin|last3=Fleischmann|first3=Martin|last4=Schreiner|first4=Andrea|last5=Seidl|first5=Michael|last6=Scheer|first6=Manfred|journal=Dalton Transactions|volume=47|issue=45|pages=16031–16035|pmid=30321246|url=https://epub.uni-regensburg.de/38440/1/Scheer%2C%20RSC%2C%20Dalton%20Transactions.pdf}}</ref> complexes and is also a useful source of unbound Cu(I).<ref name="Kubas1979" /> |
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As the coordinated acetonitrile ligands may be displaced in other solvents, the PF<sub>6</sub> compound may serve as a precursor in the non-aqueous syntheses of other Cu(I) compounds.<ref name="Kubas1979" /> Additionally, water-immiscible organic nitriles have been shown to selectively extract Cu<sup>2+</sup> from aqueous chloride solutions.<ref name="Preston1980">{{cite journal |
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| author = Preston, J.S. |
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Water-immiscible organic nitriles have been shown to selectively extract Cu(I) from aqueous chloride solutions.<ref>{{cite journal | author = Preston, J. S. |author2=Muhr D. M|author3=Parker A. J. | year = 1980 | title = Cuprous hydrometallurgy: Part VIII. Solvent extraction and recovery of copper(I) chloride with organic nitriles from an iron(III), copper(II) chloride, two-step oxidative leach of chalcopyrite concentrate | journal = ] | volume = 5|issue=2 | pages = 227| doi = 10.1016/0304-386X(80)90041-9|bibcode=1980HydMe...5..227P }}</ref> Through this method, copper can be separated from a mixture of other metals. Dilution of acetonitrile solutions with water induces disproportionation: |
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| coauthors = Muhr D.M; Parker A.J. |
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:2 <sup>+</sup> + 6 H<sub>2</sub>O → <sup>2+</sup> + Cu + 8 CH<sub>3</sub>CN |
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| year = 1980 |
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| title = Cuprous hydrometallurgy: Part VIII. Solvent extraction and recovery of copper(I) chloride with organic nitriles from an iron(III), copper(II) chloride, two-step oxidative leach of chalcopyrite concentrate |
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== See also == |
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| journal = ] |
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| volume = 5 |
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* ] |
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| issue = |
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| pages = 227 |
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| doi = 10.1016/0304-386X(80)90041-9 |
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}}</ref> Through this method, Cu<sup>+</sup>, may be isolated as <sup>+</sup> from a mixture of other metals. Furthermore, this method selectively isolated the Cu<sup>+</sup> ion from the Cu<sup>2+</sup> ion. |
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==References== |
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==References== |
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{{reflist}} |
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{{reflist}} |
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{{Hexafluorophosphates}} |
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