Misplaced Pages

Organosodium chemistry is the chemistry of organometallic compounds containing a carbon to sodium chemical bond. The application of organosodium compounds in chemistry is limited in part due to competition from organolithium compounds, which are commercially available and exhibit more convenient reactivity.

The principal organosodium compound of commercial importance is sodium cyclopentadienide. Sodium tetraphenylborate can also be classified as an organosodium compound since in the solid state sodium is bound to the aryl groups.

Organometal bonds in group 1 are characterised by high polarity with corresponding high nucleophilicity on carbon. This polarity results from the disparate electronegativity of carbon (2.55) and that of lithium 0.98, sodium 0.93 potassium 0.82 rubidium 0.82 caesium 0.79). The carbanionic nature of organosodium compounds can be minimized by resonance stabilization, for example, Ph₃CNa. One consequence of the highly polarized Na-C bond is that simple organosodium compounds often exist as polymers that are poorly soluble in solvents.

Synthesis

Transmetallation routes

In the original work the alkylsodium compound was accessed from the dialkylmercury compound by transmetallation. For example, diethylmercury in the Schorigin reaction or Shorygin reaction:

(C₂H₅)₂Hg + 2 Na → 2 C₂H₅Na + Hg

The high solubility of lithium alkoxides in hexane is the basis of a useful synthetic route:

LiCH₂SiMe₃ + NaO–t–Bu → LiOt–Bu + NaCH₂SiMe₃

Deprotonation routes

For some acidic organic compounds, the corresponding organosodium compounds arise by deprotonation. Sodium cyclopentadienide is thus prepared by treating sodium metal and cyclopentadiene:

2 Na+ 2 C₅H₆ → 2 Na C₅H₅ + H₂

Sodium acetylides form similarly. Often strong sodium bases are employed in place of the metal. Sodium methylsulfinylmethylide is prepared by treating DMSO with sodium hydride:

CH₃SOCH₃ + NaH → CH₃SOCH
₂Na + H₂

Metal-halogen exchange

Trityl sodium can be prepared by sodium-halogen exchange:

Ph₃CCl + 2 Na → Ph₃C Na + NaCl

Electron transfer

Sodium also reacts with polycyclic aromatic hydrocarbons via one-electron reduction. With solutions of naphthalene, it forms the deeply coloured radical sodium naphthalene, which is used as a soluble reducing agent:

C₁₀H₈ + Na → Na

Structural studies show however that sodium naphthalene has no Na-C bond, the sodium is invariably coordinated by ether or amine ligands. The related anthracene as well as lithium derivatives are well known.

Structures

Simple organosodium compounds such as the alkyl and aryl derivatives are generally insoluble polymers. Because of its large radius, Na prefers a higher coordination number than does lithium in organolithium compounds. Methyl sodium adopts a polymeric structure consisting of interconnected ₄ clusters. When the organic substituents are bulky and especially in the presence of chelating ligands like TMEDA, the derivatives are more soluble. For example, TMEDA is soluble in hexane. Crystals have been shown to consist of chains of alternating Na(TMEDA) and CH₂SiMe
₃ groups with Na–C distances ranging from 2.523(9) to 2.643(9) Å.

Reactions

Organosodium compounds are traditionally used as strong bases, although this application has been supplanted by other reagents such as sodium bis(trimethylsilyl)amide.

The higher alkali metals are known to metalate even some unactivated hydrocarbons and are known to self-metalate:

2 NaC₂H₅ → C₂H₄Na₂ + C₂H₆

In the Wanklyn reaction (1858) organosodium compounds react with carbon dioxide to give carboxylates:

C₂H₅Na + CO₂ → C₂H₅CO₂Na

Grignard reagents undergo a similar reaction.

Some organosodium compounds degrade by beta-elimination:

NaC₂H₅ → NaH + C₂H₄

Industrial applications

Although organosodium chemistry has been described to be of "little industrial importance", it once was central to the production of tetraethyllead. A similar Wurtz coupling-like reaction is the basis of the industrial route to triphenylphosphine:

3 PhCl + PCl₃ + 6 Na → PPh₃ + 6 NaCl

The polymerization of butadiene and styrene is catalyzed by sodium metal.

Organic derivatives of the heavier alkali metals

Organopotassium, organorubidium, and organocaesium compounds are less commonly encountered than organosodium compounds and are of limited utility. These compounds can be prepared by treatment of alkyl lithium compounds with the potassium, rubidium, and caesium alkoxides. Alternatively they arise from the organomercury compound, although this method is dated. The solid methyl derivatives adopt polymeric structures. Reminiscent of the nickel arsenide structure, MCH₃ (M = K, Rb, Cs) has six alkali metal centers bound to each methyl group. The methyl groups are pyramidal, as expected.

A notable reagent that is based on a heavier alkali metal alkyl is Schlosser's base, a mixture of n-butyllithium and potassium tert-butoxide. This reagent reacts with toluene to form the red-orange compound benzyl potassium (KCH₂C₆H₅).

Evidence for the formation of heavy alkali metal-organic intermediates is provided by the equilibration of cis-but-2-ene and trans-but-2-ene catalysed by alkali metals. The isomerization is fast with lithium and sodium, but slow with the higher alkali metals. The higher alkali metals also favor the sterically congested conformation. Several crystal structures of organopotassium compounds have been reported, establishing that they, like the sodium compounds, are polymeric.

See also

• Alkynation

References

1. Synthesis of Organometallic Compounds: A Practical Guide Sanshiro Komiya Ed. 1997
2. C. Elschenbroich, A. Salzer Organometallics : A Concise Introduction (2nd Ed) (1992) from Wiley-VCH: Weinheim. ISBN 3-527-28165-7
3. ^ Dietmar Seyferth "Alkyl and Aryl Derivatives of the Alkali Metals: Strong Bases and Reactive Nucleophiles. 2. Wilhelm Schlenk's Organoalkali-Metal Chemistry. The Metal Displacement and the Transmetalation Reactions. Metalation of Weakly Acidic Hydrocarbons. Superbases" Organometallics 2009, volume 28, pp 2–33. doi:10.1021/om801047n
4. P. Schorigin, "Beiträge zur Kenntnis der Kondensationen, welche durch Natrium bewirkt werden" Chem. Berichte 1907, vol. 40, 3111. doi:10.1002/cber.19070400371
5. P. Schorigin, "Synthesen mittels Natrium und Halogenalkylen" Ber. 41, 2711. doi:10.1002/cber.190804102208. P. Schorigin, "Über die Natriumalkyl-Verbindungen und über die mit ihrer Hilfe ausgeführten Synthesen" Berichte, 1908, vol. 41, 2717. doi:10.1002/cber.190804102209. P. Schorigin, "Synthesen mittels Natrium und Halogenalkylen" Chem. Berichte, 1908, volume 41, 2711. doi:10.1002/cber.190804102208. P. Schorigin, "Neue Synthese aromatischer Carbonsäuren aus den Kohlenwasserstoffen" Chem. Berichte 1908, vol. 41, 2723. doi:10.1002/cber.190804102210.
6. ^ William Clegg, Ben Conway, Alan R. Kennedy, Jan Klett, Robert E. Mulvey, Luca Russo "Synthesis and Structures of sodium and -potassium with Bi- and Tridentate N-Donor Ligands" Eur. J. Inorg. Chem. 2011, pp. 721–726. doi:10.1002/ejic.201000983
7. Tarun K. Panda, Michael T. Gamer, and Peter W. Roesky "An Improved Synthesis of Sodium and Potassium Cyclopentadienide" Organometallics 2003, 22, 877-878. doi:10.1021/om0207865
8. Iwai, I.; Ide, J. (1988). "2,3-Diphenyl-1,3-Butadiene". Organic Syntheses; Collected Volumes, vol. 6, p. 531.
9. ^ W. B. Renfrow Jr & C. R. Hauser (1939). "Triphenylmethylsodium". Organic Syntheses. 19: 83. doi:10.15227/orgsyn.019.0083.
10. Bock, Hans; Arad, Claudia; Näther, Christian; Havlas, Zdenek (1995). "The Structures of Solvent-Separated Naphthalene and Anthracene Radical Anions". J. Chem. Soc., Chem. Commun. (23): 2393–2394. doi:10.1039/C39950002393.
11. Vrána, Jan; Jambor, Roman; Růžička, Aleš; Dostál, Libor (2018). "New Synthetic Strategies Leading to [RNPNR]− Anions and the Isolation of the [P(Nt-Bu)3]3− Trianion". Dalton Transactions. 47 (25): 8434–8441. doi:10.1039/C8DT02141D. PMID 29897357.
12. ^ E. Weiss, "Structures of Organo Alkali Metal Complexes and Related Compounds" Angewandte Chemie International Edition in English, 1993, volume 32, pages 1501–1523. doi:10.1002/anie.199315013
13. Schümann, Uwe; Behrens, Ulrich; Weiss, Erwin (April 1989). "Synthese und Struktur von Bis, einem Phenylnatrium-Solvat". Angewandte Chemie. 101 (4): 481–482. Bibcode:1989AngCh.101..481S. doi:10.1002/ange.19891010420.
14. J. A. Wanklyn, Ann. 107, 125 (1858)
15. The Merck index of chemicals and drugs: an encyclopedia for chemists, Paul G. Stecher
16. Rolf Ackermann, Ludwig Lange "Sodium Compounds, Organic" in Ullmann's Encyclopedia of Industrial Chemistry, 2005 Wiley-VCH, Weinheim. doi:10.1002/14356007.a24_341
17. Manfred Schlosser (1988). "Superbases for organic synthesis". Pure Appl. Chem. 60 (11): 1627–1634. doi:10.1351/pac198860111627.

v t e Compounds of carbon with other elements in the periodic table
CH He CLi CBe CB CC CN CO CF Ne CNa CMg CAl CSi CP CS CCl CAr CK CCa CSc CTi CV CCr CMn CFe CCo CNi CCu CZn CGa CGe CAs CSe CBr CKr CRb CSr CY CZr CNb CMo CTc CRu CRh CPd CAg CCd CIn CSn CSb CTe CI CXe CCs CBa CLu CHf CTa CW CRe COs CIr CPt CAu CHg CTl CPb CBi CPo CAt Rn Fr CRa Lr Rf Db CSg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og   CLa CCe CPr CNd CPm CSm CEu CGd CTb CDy CHo CEr CTm CYb Ac CTh CPa CU CNp CPu CAm CCm CBk CCf CEs Fm Md No
Legend	Chemical bonds to carbon Core organic chemistry Many uses in chemistry Academic research, no widespread use Bond unknown

• Organosodium compounds