Corannulene

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Corannulene
Corannulene.svg
Corannulene3D.png
Identifiers
CAS number 5821-51-2 YesY
PubChem 11831840
ChemSpider 10006487 YesY
Jmol-3D images Image 1
Image 2
Properties
Molecular formula C20H10
Molar mass 250.29 g/mol
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Corannulene is a polycyclic aromatic hydrocarbon with chemical formula C20H10.[1] The molecule consists of a cyclopentane ring fused with 5 benzene rings, so another name for it is [5]circulene. It is of scientific interest because it is a geodesic polyarene and can be considered a fragment of buckminsterfullerene. Due to this connection and also its bowl shape, corannulene is also known as a buckybowl. Corannulene exhibits a bowl-to-bowl inversion with an inversion barrier of 10.2 kcal/mol (42.7 kJ/mol) at −64 °C.[2]

Synthesis[edit]

Several synthetic routes exist to corannulene. Flash vacuum pyrolysis techniques generally have lower chemical yields than solution-chemistry syntheses, but offer routes to more derivatives. Corannulane was first isolated in 1966 by multistep organic synthesis.[3] A flash vacuum pyrolysis method followed in 1991.[4] One synthesis based on solution chemistry[5] consists of a nucleophilic displacementelimination reaction of an octabromide with potassium hydroxide:

Corannulene synthesis Sygula 2000

The bromine substituents are removed with an excess of n-butyllithium.

Much effort is directed at functionalization of the corannulene ring with novel functional groups such as ethynyl groups,[2][6][7] ether groups,[8] thioether groups,[9] platinum functional groups,[10] aryl groups,[11] phenalenyl fused [12] and indeno extensions.[13] and ferrocene groups.[14]

Aromaticity[edit]

The observed aromaticity for this compound is explained with a so-called annulene-within-an-annulene model. According to this model corannulene is made up of an aromatic 6 electron cyclopentadienyl anion surrounded by an aromatic 14 electron annulenyl cation. This model was suggested by Barth and Lawton in the first synthesis of corannulene in 1966.[3] They also suggested the trivial name 'corannulene', which is derived from the annulene-within-an-annulene model: core + annulene.

annulene-within-an-annulene model

However, later theoretical calculations have disputed the validity of this approximation.[15][16]

Reactions[edit]

Reduction[edit]

Corannulene can be reduced up to a tetraanion in a series of one-electron reductions. This has been performed with alkali metals, electrochemically and with bases. The corannulene dianion is antiaromatic and tetraanion is again aromatic. With lithium as reducing agent two tetraanions form a supramolecular dimer with two bowls stacked into each other with 4 lithium ions in between and 2 pairs above and below the stack.[17] This self-assembly motif was applied in the organization of fullerenes. Penta-substituted fullerenes (with methyl or phenyl groups) charged with five electrons form supramolecular dimers with a complementary corannulene tetraanion bowl, 'stitched' by interstitial lithium cations.[18] In a related system 5 lithium ions are sandwiched between two corannulene bowls [19]

In one cyclopenta[bc]corannulene a concave - concave aggregate is observed by NMR spectroscopy with 2 C–Li–C bonds connecting the tetraanions.[20]

Cyclopenta[bc]corannulene

Metals tend to bind to the convex face of the annulene. Concave binding has been reported for a cesium / crown ether system [21]

Oxidation[edit]

UV 193-nm photoionization effectively removes a π-electron from the twofold degenerate E1-HOMO located in the aromatic network of electrons yielding a corannulene radical cation.[22] Owing to the degeneracy in the HOMO orbital, the corannulene radical cation is unstable in its original C5v molecular arrangement, and therefore, subject to Jahn-Teller (JT) vibronic distortion.

Using electrospray ionization, a protonated corannulene cation has been produced in which the protonation site was observed to be on a peripheral sp2-carbon atom.[22]

Reaction with electrophiles[edit]

Corannulene can react with electrophiles to form a corannulene carbocation. Reaction with chloromethane and aluminium chloride results in the formation of an AlCl4- salt with a methyl group situated at the center with the cationic center at the rim. X-ray diffraction analysis shows the that the new carbon-carbon bond is elongated (157 pm) [23]


Bicorannulenyl[edit]

Bicorannulenyl is the product of dehydrogenative coupling of corannulene. With the formula C20H9-C20H9, it consists of two corannulene units connected through a single C-C bond. The molecule's stereochemistry consists of two chiral elements: the asymmetry of a singly substituted corannulenyl, and the helical twist about the central bond. In the neutral state, bicorannulenyl exists as 12 conformers, which intercovert through multiple bowl-inversions and bond-rotations.[24] When bicorannulenyl is reduced to a dianion with potassium metal, the central bond assumes significant double-bond character. This change is attributed to the orbital structure, which has a LUMO orbital localized on the central bond.[25] When bicorannulenyl is reduced to an octaanion with lithium metal, it self-assembles into supramolecular oligomers.[26] This motif illustrates "charged polyarene stacking".

Research[edit]

The buckycatcher

The corannulene group is used in host-guest chemistry with interactions based on pi stacking, notably with fullerenes (the buckycatcher) [27][28] but also with nitrobenzene [29]

Alkyl-substituted corannulenes form a thermotropic hexagonal columnar liquid crystalline mesophase.[30] Corannulenes also been used as the core group in a dendrimer.[11] Like other PAHs, corannulene serveds as a ligand to metals.[31][32][33][34][35][36][37] Corannulenes with ethynyl groups are investigated for their potential use as blue emitters.[7]

In space[edit]

Although corannulene has not yet been detected in interstellar space,[38][39] more than 20% of the carbon in the universe may be associated with polycyclic aromatic hydrocarbons.[40]

See also[edit]

References[edit]

  1. ^ Scott, L. T.; Bronstein, H. E.; Preda, D. V.; Ansems, R. B. M.; Bratcher, M. S.; Hagen, S. (1999). "Geodesic polyarenes with exposed concave surfaces". Pure and Applied Chemistry 71 (2): 209. doi:10.1351/pac199971020209.  edit
  2. ^ a b Scott, L. T.; Hashemi, M. M.; Bratcher, M. S. (1992). "Corannulene bowl-to-bowl inversion is rapid at room temperature". Journal of the American Chemical Society 114 (5): 1920. doi:10.1021/ja00031a079.  edit
  3. ^ a b Barth, W. E.; Lawton, R. G. (1966). "Dibenzo[ghi,mno]fluoranthene". Journal of the American Chemical Society 88 (2): 380. doi:10.1021/ja00954a049.  edit
  4. ^ Scott, L. T.; Hashemi, M. M.; Meyer, D. T.; Warren, H. B. (1991). "Corannulene. A convenient new synthesis". Journal of the American Chemical Society 113 (18): 7082. doi:10.1021/ja00018a082.  edit
  5. ^ Sygula, A.; Rabideau, P. W. (2000). "A Practical, Large Scale Synthesis of the Corannulene System". Journal of the American Chemical Society 122 (26): 6323. doi:10.1021/ja0011461.  edit
  6. ^ Wu, Y.; Bandera, D.; Maag, R.; Linden, A.; Baldridge, K.; Siegel, J. (2008). "Multiethynyl corannulenes: synthesis, structure, and properties". Journal of the American Chemical Society 130 (32): 10729–10739. doi:10.1021/ja802334n. PMID 18642812.  edit
  7. ^ a b Mack, J.; Vogel, P.; Jones, D.; Kaval, N.; Sutton, A. (2007). "The development of corannulene-based blue emitters". Organic & biomolecular chemistry 5 (15): 2448–2452. doi:10.1039/b705621d. PMID 17637965.  edit
  8. ^ Gershoni-Poranne, R.; Pappo, D.; Solel, E.; Keinan, E. (2009). "Corannulene ethers via Ullmann condensation". Organic Letters 11 (22): 5146–5149. doi:10.1021/ol902352k. PMID 19905024.  edit
  9. ^ Baldridge, K.; Hardcastle, K.; Seiders, T.; Siegel, J. (2010). "Synthesis, structure and properties of decakis(phenylthio)corannulene". Organic & biomolecular chemistry 8 (1): 53–55. doi:10.1039/b919616a. PMID 20024131.  edit
  10. ^ Choi, H.; Kim, C.; Park, K. M.; Kim, J.; Kang, Y.; Ko, J. (2009). "Synthesis and structure of penta-platinum σ-bonded derivatives of corannulene". Journal of Organometallic Chemistry 694 (22): 3529. doi:10.1016/j.jorganchem.2009.07.015.  edit
  11. ^ a b Pappo, D.; Mejuch, T.; Reany, O.; Solel, E.; Gurram, M.; Keinan, E. (2009). "Diverse Functionalization of Corannulene: Easy Access to Pentagonal Superstructure". Organic Letters 11 (5): 1063–1066. doi:10.1021/ol8028127. PMID 19193048.  edit
  12. ^ Nishida, S.; Morita, Y.; Ueda, A.; Kobayashi, T.; Fukui, K.; Ogasawara, K.; Sato, K.; Takui, T.; Nakasuji, K. (2008). "Curve-structured phenalenyl chemistry: synthesis, electronic structure, and bowl-inversion barrier of a phenalenyl-fused corannulene anion". Journal of the American Chemical Society 130 (45): 14954–14955. doi:10.1021/ja806708j. PMID 18937470.  edit
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  14. ^ Corannulenylferrocenes: towards a 1D, non-covalent metal–organic nanowire Berit Topolinski , Bernd M. Schmidt , Michael Kathan , Sergej I. Troyanov and Dieter Lentz Chem. Commun., 2012,48, 6298-6300 doi:10.1039/C2CC32275G
  15. ^ Sygula, A.; Rabideau, P. W. (1995). "Structure and inversion barriers of corannulene, its dianion and tetraanion. An ab initio study". Journal of Molecular Structure: THEOCHEM 333 (3): 215–226. doi:10.1016/0166-1280(94)03961-J.  edit
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  17. ^ Ayalon, A.; Sygula, A.; Cheng, P.; Rabinovitz, M.; Rabideau, P.; Scott, L. (1994). "Stable High-Order Molecular Sandwiches: Hydrocarbon Polyanion Pairs with Multiple Lithium Ions Inside and out". Science 265 (5175): 1065–1067. Bibcode:1994Sci...265.1065A. doi:10.1126/science.265.5175.1065. PMID 17832895.  edit
  18. ^ Aprahamian, I.; Eisenberg, D.; Hoffman, R.; Sternfeld, T.; Matsuo, Y.; Jackson, E.; Nakamura, E.; Scott, L.; Sheradsky, T.; Rabinovitz, M. (2005). "Ball-and-socket stacking of supercharged geodesic polyarenes: bonding by interstitial lithium ions". Journal of the American Chemical Society 127 (26): 9581–9587. doi:10.1021/ja0515102. PMID 15984885.  edit
  19. ^ A Main Group Metal Sandwich: Five Lithium Cations Jammed Between Two Corannulene Tetraanion Decks Zabula, et al. Science 19 August 2011: 1008-1011. doi:10.1126/science.1208686
  20. ^ Aprahamian, I.; Preda, D.; Bancu, M.; Belanger, A.; Sheradsky, T.; Scott, L.; Rabinovitz, M. (2006). "Reduction of bowl-shaped hydrocarbons: dianions and tetraanions of annelated corannulenes". The Journal of Organic Chemistry 71 (1): 290–298. doi:10.1021/jo051949c. PMID 16388648.  edit
  21. ^ Spisak, S. N., Zabula, A. V., Filatov, A. S., Rogachev, A. Y. and Petrukhina, M. A. (2011), Selective Endo and Exo Binding of Alkali Metals to Corannulene. Angewandte Chemie International Edition, 50: 8090–8094. doi:10.1002/anie.201103028
  22. ^ a b Galué, Héctor Alvaro; Rice, Corey A.; Steill, Jeffrey D.; Oomens, Jos (1 January 2011). "Infrared spectroscopy of ionized corannulene in the gas phase". The Journal of Chemical Physics 134 (5): 054310. Bibcode:2011JChPh.134e4310G. doi:10.1063/1.3540661. 
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  26. ^ Eisenberg, D., Quimby, J. M., Jackson, E. A., Scott, L. T. and Shenhar, R. (2010), Highly Charged Supramolecular Oligomers Based on the Dimerization of Corannulene Tetraanion. Chemical Communications, 46: 9010–9012. doi:10.1039/c0cc03965a
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  32. ^ d8 Rhodium and Iridium Complexes of Corannulene Jay S. Siegel, Kim K. Baldridge, Anthony Linden, and Reto Dorta J. Am. Chem. Soc., 2006, 128 (33), pp 10644–10645 doi:10.1021/ja062110x
  33. ^ Petrukhina, M. A. (2008). "Coordination of buckybowls: the first concave-bound metal complex". Angewandte Chemie (International ed. in English) 47 (9): 1550–1552. doi:10.1002/anie.200704783. PMID 18214869.  edit
  34. ^ Zhu, B.; Ellern, A.; Sygula, A.; Sygula, R.; Angelici, R. J. (2007). "η6-Coordination of the Curved Carbon Surface of Corannulene (C20H10) to (η6-arene)M2+(M = Ru, Os)". Organometallics 26 (7): 1721. doi:10.1021/om0610795.  edit
  35. ^ Petrukhina, M. A.; Sevryugina, Y.; Rogachev, A. Y.; Jackson, E. A.; Scott, L. T. (2006). "Corannulene:  A Preference forexo-Metal Binding. X-ray Structural Characterization of [Ru2(O2CCF3)2(CO)4·(η2-C20H10)2]". Organometallics 25 (22): 5492. doi:10.1021/om060350f.  edit
  36. ^ Siegel, J.; Baldridge, K.; Linden, A.; Dorta, R. (2006). "D8 rhodium and iridium complexes of corannulene". Journal of the American Chemical Society 128 (33): 10644–10645. doi:10.1021/ja062110x. PMID 16910635.  edit
  37. ^ Bandera, D., Baldridge, K. K., Linden, A., Dorta, R. and Siegel, J. S. (2011), Stereoselective Coordination of C5-Symmetric Corannulene Derivatives with an Enantiomerically Pure [RhI(nbd*)] Metal Complex. Angewandte Chemie International Edition, 50: 865–867. doi:10.1002/anie.201006877
  38. ^ Pilleri, P.; Herberth, D.; Giesen, T. F.; Gerin, M.; Joblin, C.; Mulas, G.; Malloci, G.; Grabow, J. -U.; Brünken, S.; Surin, L.; Steinberg, B. D.; Curtis, K. R.; Scott, L. T. (2009). "Search for corannulene (C20H10) in the Red Rectangle". Monthly Notices of the Royal Astronomical Society 397 (2): 1053. arXiv:0905.1845. Bibcode:2009MNRAS.397.1053P. doi:10.1111/j.1365-2966.2009.15067.x.  edit
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