| Revision as of 12:09, 10 March 2011 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Script assisted update of identifiers from ChemSpider, CommonChemistry and FDA for the Chem/Drugbox validation project - Updated: InChI InChIKey.← Previous edit |
Latest revision as of 23:25, 16 December 2024 edit undoLeo51db (talk | contribs)2 edits Image of anion replaced with picture of real life product as the structure is already well represented in the other pictures. |
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{{Redirect|NaCp|other uses|NACP (disambiguation)}} |
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{{merge|Cyclopentadienyl radical|Cyclopentadienyl anion|discuss=Talk: Cyclopentadienyl anion#Merge proposal|date=November 2024}} |
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{{chembox |
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{{chembox |
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|Watchedfields = changed |
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| verifiedrevid = 396513994 |
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|verifiedrevid = 418117276 |
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|ImageFile=Sodium cyclopentadienide.png |
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|ImageFile = Sodium cyclopentadiene.svg |
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|ImageSize= |
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|ImageSize = 100px |
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|ImageFile2=NaCp-chain-from-xtal-3D-balls-C.png |
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|ImageFile1 = NaCp-chain-from-xtal-3D-balls-C.png |
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|ImageSize2=250px |
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|ImageFileL2 = NaCp-xtal-3D-SF-A.png |
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|IUPACName= |
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|ImageFileR2 = NaCp-xtal-3D-SF-B.png |
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|OtherNames= sodium cyclopentadienylide, cyclopentadienylsodium |
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|ImageFile3 = NaCp Product2.jpg |
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|ImageCaption3 = NaCp synthesized in an inert atmosphere |
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|PIN = Sodium cyclopentadienide |
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|OtherNames = Sodium cyclopentadienylide, Cyclopentadienylsodium |
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|Section1={{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/C5H5.Na/c1-2-4-5-3-1;/h1-5H;/q-1;+1 |
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|StdInChI = 1S/C5H5.Na/c1-2-4-5-3-1;/h1-5H;/q-1;+1 |
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| StdInChIKey = OHUVHDUNQKJDKW-UHFFFAOYSA-N |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| InChI = 1S/C5H5.Na/c1-2-4-5-3-1;/h1-5H;/q-1;+1 |
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| InChIKey1 = OHUVHDUNQKJDKW-UHFFFAOYSA-N |
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|StdInChIKey = OHUVHDUNQKJDKW-UHFFFAOYSA-N |
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|InChI = 1S/C5H5.Na/c1-2-4-5-3-1;/h1-5H;/q-1;+1 |
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| CASNo=4984-82-1 |
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|InChIKey1 = OHUVHDUNQKJDKW-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|CASNo = 4984-82-1 |
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| PubChem=78681 |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| EINECS=225-636-8 |
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|PubChem = 78681 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|EINECS = 225-636-8 |
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| ChemSpiderID=71032 |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| SMILES = .c1ccc1 |
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|ChemSpiderID = 71032 |
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|SMILES = .c1ccc1 |
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|Section2={{Chembox Properties |
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|Section2={{Chembox Properties |
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| C=5 | H = 5| Na = 1 |
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|C=5 | H=5 | Na=1 |
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| Appearance= |
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|Appearance=colorless solid |
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| Density= |
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|Density=1.113 g/cm<sup>3</sup> |
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|Solubility=decomposition |
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|SolubleOther=] |
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}} |
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| Solubility=Reacts |
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| SolubleOther=Soluble |
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| Solvent=] |
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}} |
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|Section3={{Chembox Hazards |
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|Section3={{Chembox Hazards |
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| MainHazards= |
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|MainHazards=flammable |
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| FlashPt= |
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'''Sodium cyclopentadienide''' is an ] with the ] C<sub>5</sub>H<sub>5</sub>Na. The compound is often abbreviated as NaCp or CpNa, where Cp<sup>−</sup> is the ]. Cp is also used as an abbreviation for the ] ] in ].<ref>{{RedBookRef2005|page=262}}</ref> |
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'''Sodium cyclopentadienide''' is an ] with the ] C<sub>5</sub>H<sub>5</sub>Na. The compound is often abbreviated as NaCp, where Cp<sup>−</sup> is the cyclopentadienide anion.<ref>{{RedBookRef2005|page=262}}</ref> Sodium cyclopentadienide is a colorless solid, although samples often are pink owing to traces of oxidized impurities.<ref name= Roesky/> |
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==Preparation== |
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==Preparation== |
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Sodium cyclopentadienide is commercially available as a solution in ]. It is prepared by treating ] with ]:<ref>{{Cotton&Wilkinson5th|page=139}}</ref> |
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Sodium cyclopentadienide is commercially available as a solution in ]. It is prepared by treating ] with ]:<ref>{{Cotton&Wilkinson5th|page=139}}</ref> |
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:{{chem2|2 Na + 2 C5H6 -> 2 NaC5H5 + H2}} |
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:2 Na + 2 C<sub>5</sub>H<sub>6</sub> → 2 NaC<sub>5</sub>H<sub>5</sub> + ] |
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Commonly, the conversion is conducted by heating a suspension of molten sodium in ].<ref>Tarun K. Panda, Michael T. Gamer, Peter W. Roesky "An Improved Synthesis of Sodium and Potassium Cyclopentadienide" Organometallics, 2003, 22, 877–878.{{DOI|10.1021/om0207865}}</ref> In former times, the sodium was provided in the form of "sodium wire" or "sodium sand", a fine dispersion of sodium prepared by melting sodium in refluxing ] and rapidly stirring, was common.<ref name = ferrocene>{{OrgSynth | title = Ferrocene | author = ] | collvol = 4 | collvolpages = 473 | year = 1963 | prep = cv4p0473}}</ref><ref>{{OrgSynth | author = Partridge, John J.; Chadha, Naresh K.; Uskokovic, Milan R. | title = An asymmetric hydroboration of 5-substituted cyclopentadienes: synthesis of methyl (1''R'',5''R'')-5-hydroxy-2-cyclopentene-1-acetate | collvol = 7 | collvolpages = 339 | prep = cv7p0339 | year = 1990}}</ref> ] is a convenient base:<ref>Girolami, G. S.; Rauchfuss, T. B. and Angelici, R. J., Synthesis and Technique in Inorganic Chemistry, University Science Books: Mill Valley, CA, 1999.ISBN 0935702482</ref> |
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The conversion can be conducted by heating a suspension of molten sodium in ].<ref name= Roesky>Tarun K. Panda, Michael T. Gamer, Peter W. Roesky "An Improved Synthesis of Sodium and Potassium Cyclopentadienide" Organometallics, 2003, 22, 877–878.{{doi|10.1021/om0207865}}</ref> In former times, the sodium was provided in the form of "sodium wire" or "sodium sand", a fine dispersion of sodium prepared by melting sodium in refluxing ] and rapidly stirring.<ref name = ferrocene>{{OrgSynth | title = Ferrocene | author = ] | collvol = 4 | collvolpages = 473 | year = 1963 | prep = cv4p0473}}</ref><ref>{{OrgSynth | author = Partridge, John J.; Chadha, Naresh K.; Uskokovic, Milan R. | title = An asymmetric hydroboration of 5-substituted cyclopentadienes: synthesis of methyl (1''R'',5''R'')-5-hydroxy-2-cyclopentene-1-acetate | collvol = 7 | collvolpages = 339 | prep = cv7p0339 | year = 1990}}</ref> ] is a convenient base:<ref>{{cite book |author1=Girolami, G. S. |author2=Rauchfuss, T. B. |author3=Angelici, R. J. |author1-link=Gregory S. Girolami |author3-link=Robert Angelici |name-list-style=amp | title = Synthesis and Technique in Inorganic Chemistry | publisher = University Science Books: Mill Valley | location = CA | year = 1999 | isbn = 0935702482}}</ref> |
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:{{chem2|NaH + 2 C5H6 -> NaC5H5 + H2}} |
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:NaH + C<sub>5</sub>H<sub>6</sub> → NaC<sub>5</sub>H<sub>5</sub> + H<sub>2</sub> |
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In early work, ]s were used as bases. With a ] of 15, cyclopentadiene can be deprotonated by many reagents. |
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In early work, ]s were used as bases. With a ] of 15, cyclopentadiene can be deprotonated by many reagents. |
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The nature of NaCp depends strongly its medium and for the purposes of planning syntheses, the reagent is often represented as a salt Na<sup>+</sup>C<sub>5</sub>H<sub>5</sub><sup>−</sup>. Crystalline solvent-free NaCp, which is rarely encountered, is a "polydecker" ], consisting of an infinite chain of alternating Na<sup>+</sup> centers sandwiched between ]-]:η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub> ligands.<ref>{{cite journal | author = Robert E. Dinnebier, Ulrich Behrens, and Falk Olbrich | title = Solid State Structures of Cyclopentadienyllithium, -sodium, and -potassium. Determination by High-Resolution Powder Diffraction | journal = ] | year = 1997 | volume = 16 | pages = 3855–3858 | doi = 10.1021/om9700122}}</ref> As a solution in donor solvents, NaCp is highly solvated, especially at the alkali metal as suggested by the isolability of the ] Na(])Cp.<ref>Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim. ISBN 978-3-29390-6</ref> |
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==Applications== |
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==Applications== |
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Sodium cyclopentadienide is a common reagent for the preparation of ]s. For example, the preparation of ]<ref name = ferrocene/> and ]:<ref>{{cite journal | author = ]; Birmingham, J. G. | year = 1954 | title = Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta | journal = ] | volume = 76 | issue = 17 | pages = 4281–84 | doi = 10.1021/ja01646a008}}</ref> |
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Sodium cyclopentadienide is a common reagent for the preparation of ]s. For example, the preparation of ]<ref name = ferrocene/> and ]:<ref>{{cite journal |author1=Wilkinson, G. |author2=Birmingham, J. G. | year = 1954 | title = Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta | journal = ] | volume = 76 | issue = 17 | pages = 4281–84 | doi = 10.1021/ja01646a008|bibcode=1954JAChS..76.4281W |author1-link=Geoffrey Wilkinson }}</ref> |
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:{{Chem2|2 NaC5H5 + FeCl2 -> Fe(C5H5)2 + 2 NaCl}} |
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:2 NaC<sub>5</sub>H<sub>5</sub> + ] → Fe(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> + 2 NaCl |
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:ZrCl<sub>4</sub>(thf)<sub>2</sub> + 2 NaCp → Cp<sub>2</sub>ZrCl<sub>2</sub> + 2 NaCl + 2 THF |
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:{{chem2|ZrCl4(thf)2 + 2 NaCp -> (C5H5)2ZrCl2 + 2 NaCl + 2 THF}} |
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Sodium cyclopentadienide is also used for the preparation of substituted cyclopentadienyl derivatives such as the ester and formyl derivatives:<ref>{{cite journal|author1=Macomber, D. W. |author2=Hart, W. P. |author3=Rausch, M. D. |title=Functionally Substituted Cyclopentadienyl Metal Compounds|journal=Adv. Organomet. Chem.|year=1982|volume=21|pages=1–55|doi=10.1016/S0065-3055(08)60377-9|series=Advances in Organometallic Chemistry |isbn=9780120311217}}</ref> |
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:{{chem2|NaC5H5 + O\dC(OEt)2 → NaC5H4CO2Et + NaOEt}} |
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These compounds are used to prepare substituted metallocenes such as ].<ref>{{cite journal |doi=10.1021/om4004972|title=Large-Scale Preparation of 1,1′-Ferrocenedicarboxylic Acid, a Key Compound for the Synthesis of 1,1′-Disubstituted Ferrocene Derivatives |year=2013 |last1=Petrov |first1=Alex R. |last2=Jess |first2=Kristof |last3=Freytag |first3=Matthias |last4=Jones |first4=Peter G. |last5=Tamm |first5=Matthias |journal=Organometallics |volume=32 |issue=20 |pages=5946–5954}}</ref> |
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==Structure== |
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The nature of NaCp depends strongly on its medium and for the purposes of planning syntheses; the reagent is often represented as a salt {{chem|Na|+|C|5|H|5|-}}. Crystalline solvent-free NaCp, which is rarely encountered, is a "polydecker" ], consisting of an infinite chain of alternating Na<sup>+</sup> centers sandwiched between ]-]:''η''<sup>5</sup>-C<sub>5</sub>H<sub>5</sub> ligands.<ref>{{cite journal |author1=Robert E. Dinnebier |author2=Ulrich Behrens |author3=Falk Olbrich |name-list-style=amp | title = Solid State Structures of Cyclopentadienyllithium, -sodium, and -potassium. Determination by High-Resolution Powder Diffraction | journal = ] | year = 1997 | volume = 16 |issue=17 | pages = 3855–3858 | doi = 10.1021/om9700122}}</ref> As a solution in donor solvents, NaCp is highly solvated, especially at the alkali metal as suggested by the isolability of the ] Na(])Cp.<ref>{{cite book | author = Elschenbroich, C. | title = Organometallics | year = 2006 | publisher = Wiley-VCH: Weinheim | isbn = 978-3-527-29390-2}}</ref> |
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In contrast to alkali metal cyclopentadienides, ] cyclopentadienide (Bu<sub>4</sub>N<sup>+</sup>C<sub>5</sub>H<sub>5</sub><sup>−</sup>) was found to be supported entirely by ionic bonding and its structure is representative of the structure of the cyclopentadienide anion (C<sub>5</sub>H<sub>5</sub><sup>−</sup>, Cp<sup>−</sup>) in the solid state. However, the anion deviates somewhat from a planar, regular pentagon, with C–C bond lengths ranging from 138.0 -140.1 pm and C–C–C bond angles ranging from 107.5-108.8°.<ref>{{cite journal|last1=Reetz|first1=Manfred T.|last2=Hütte|first2=Stephan|last3=Goddard|first3=Richard|date=1995-03-01|title=Tetrabutylammonium Salts of 2-Nitropropane, Cyclopentadiene and 9-Ethylfluorene: Crystal Structures and Use in Anionic Polymerization|journal=Zeitschrift für Naturforschung B|language=en|volume=50|issue=3|pages=415–422|doi=10.1515/znb-1995-0316|s2cid=45791403 |issn=1865-7117|doi-access=free}}</ref> |
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==See also== |
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==References== |
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==References== |
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{{reflist}} |
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<references/> |
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{{Cyclopentadiene complexes}} |
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