Möbius aromaticity

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Möbius versus Hückel

In organic chemistry, Möbius aromaticity is a special type of aromaticity believed to exist in a number of organic molecules. [1] [2] In terms of molecular orbital theory these compounds have in common a monocyclic array of molecular orbitals in which there is an odd number of out-of-phase overlaps, the opposite pattern compared to the aromatic character to Hückel systems. The spatial configuration of the orbitals is reminiscent of a Möbius strip, hence the name. The smallest member of this class of compounds would be trans-benzene. Möbius molecular systems were considered in 1964 by Edgar Heilbronner by application of the Hückel method,[3] but the first such compound was not synthesized until 2003 by the group of Rainer Herges.[4]


Hückel-Möbius aromaticity[edit]

The Herges compound (6 in the image below) was synthesized in several photochemical cycloaddition reactions from tetradehydrodianthracene 1 and the ladderane syn-tricyclooctadiene 2 as a substitute for cyclooctatetraene.[5]

Synthesis of a Mobius ring

Intermediate 5 was a mixture of 2 isomers and the final product 6 a mixture of 5 isomers with different cis and trans configurations. One of them was found to have a C2 molecular symmetry corresponding to a Möbius aromatic and another Hückel isomer was found with Cs symmetry. Despite having 16 electrons in its pi system (making it a 4n antiaromatic compound) the Heilbronner prediction was borne out because according to Herges the Möbius compound was found to have aromatic properties. With bond lengths deduced from X-ray crystallography a HOMA value was obtained of 0.50 (for the polyene part alone) and 0.35 for the whole compound which qualifies it as a moderate aromat.

It was pointed out by Henry Rzepa that the conversion of intermediate 5 to 6 can proceed by either a Hückel or a Möbius transition state.[6]

Huckel vs Mobius Transition State

The difference was demonstrated in a hypothetical pericyclic ring opening reaction to cyclododecahexaene. The Hückel TS (left) involves 6 electrons (arrow pushing in red) with Cs molecular symmetry conserved throughout the reaction. The ring opening is disrotatory and suprafacial and both bond length alternation and NICS values indicate that the 6 membered ring is aromatic. The Möbius TS with 8 electrons on the other hand has lower computed activation energy and is characterized by C2 symmetry, a conrotatory and antarafacial ring opening and 8-membered ring aromaticity.

Another interesting system is the cyclononatetraenyl cation explored for over 30 years by Paul v. R. Schleyer et al. This reactive intermediate is implied in the solvolysis of the bicyclic chloride 9-deutero-9'-chlorobicyclo[6.1.0]-nonatriene 1 to the indene dihydroindenol 4.[7][8] The starting chloride is deuterated in only one position but in the final product deuterium is distributed at every available position. This observation is explained by invoking a twisted 8-electron cyclononatetraenyl cation 2 for which a NICS value of -13.4 (outsmarting benzene) is calculated.[9]

the cyclononatetraenyl cation

In 2005 the same P. v. R. Schleyer [10] questioned the 2003 Herges claim: he analyzed the same crystallographic data and concluded that there was indeed a large degree of bond length alternation resulting in a HOMA value of -0.02, a computed NICS value of -3.4 ppm also did not point towards aromaticity and (also inferred from a computer model) steric strain would prevent effective pi-orbital overlap.

A Hückel-Möbius aromaticity switch (2007) has been described based on a 28 pi-electron porphyrin system:[11][12]

Hückel-Möbius aromaticity switch

The phenylene rings in this molecule are free to rotate forming a set of conformers: one with a Möbius half-twist and another with a Hückel double-twist (a figure-eight configuration) of roughly equal energy.

In 2014, Zhu and Xia (with the help of Schleyer) synthesized a planar Möbius system that consisted of two pentene rings connected with an osmium atom.[13] They formed derivatives where osmium had 16 and 18 electrons and determined that Craig–Möbius aromaticity is more important for the stabilization of the molecule than the metal's electron count.

Transition states[edit]

Möbius systems are also found in transition states. The determination of a transition state as Möbius or Hückel is involved in deciding if a reaction with 4N or 4N+2 electrons is allowed or forbidden. This uses the Möbius-Hückel concept.[14][15]

Ansatz Wavefunction & Hückel-Möbius Energy[edit]

For the Mobius geometry, the boundary conditions differ from the standard particle in a ring problem. Supposing to have a strip of length and , we can see that general Mobius boundary conditions for the wavefunction are:

or using the spherical azimuthal angle :

For an -carbons, the proposed ansatz linear combination of atomic orbitals (LCAO) is:

where is the angle at each -th carbon atom and is the -th AO. Thus, for circular carbon rings, the general Mobius boundary condition can be rewritten as:

Using this equation and the Euler rule we can find the right value satisfying previous boundary conditions:

From the last equation we see that to fulfil the general boundary conditions, must be a half-integer number. The coefficients of the ansatz become:

From figure above, it can also be seen that the overlap between two consecutive AOs is at a constant angle , and for this reason resonance integral it's considered as a constant into the Huckel matrix we will write later. It could be simply written as:

where is the standard Huckel’s resonance integral value (the one with ). Nevertheless, the presence of a axis as the only symmetry element brings to a full phase change at the end of the ring, e.i. between the first and the -th carbon atoms. For this reason, in the Huckel matrix the resonance integral between carbon and is .
For the generic carbons Mobius system, the Huckel matrix is:

Eigenvalues equation can now be solved. Since is a matrix, we will have eigenvalues and MOs. Defining the variable

we have:

Hence we obtain a system of equations, in which the first one () and the last one () have a coefficient:

All these equations can be easily solved using Euler's rule, leading to

hence


See also[edit]

References[edit]

  1. ^ Möbius Aromaticity and Delocalization Henry S. Rzepa Chem. Rev., 2005, 105 (10), pp 3697–3715 doi:10.1021/cr030092l
  2. ^ Möbius aromaticity and antiaromaticity in expanded porphyrins Zin Seok Yoon, Atsuhiro Osuka & Dongho Kim Nature Chemistry 1, 113 - 122 (2009) doi:10.1038/nchem.172
  3. ^ Hückel molecular orbitals of Möbius-type conformations of annulenes Tetrahedron Letters, Volume 5, Issue 29, 1964, Pages 1923-1928 E. Heilbronner doi:10.1016/S0040-4039(01)89474-0
  4. ^ Synthesis of a Möbius aromatic hydrocarbon D. Ajami, O. Oeckler, A. Simon, R. Herges Nature 426, 819-821 (18 December 2003) doi:10.1038/nature02224 PMID 14685233
  5. ^ Note that the Möbius ring is formed in formal metathesis reaction between 1 and COT
  6. ^ The Aromaticity of Pericyclic Reaction Transition States Henry S. Rzepa J. Chem. Educ. 2007, 84, 1535. Abstract
  7. ^ Thermal bicyclo[6.1.0]nonatrienyl chloride-dihydroindenyl chloride rearrangement Paul v. R. Schleyer, James C. Barborak, Tah Mun Su, Gernot Boche, and G. Schneider J. Am. Chem. Soc.; 1971; 93(1) pp 279 - 281; doi:10.1021/ja00730a063
  8. ^ Topology in Chemistry: Designing Möbius Molecules Herges, R. Chem. Rev.; (Review); 2006; 106(12); 4820-4842. doi:10.1021/cr0505425
  9. ^ Monocyclic (CH)9+ - A Heilbronner Möbius Aromatic System Revealed Angewandte Chemie International Edition Volume 37, Issue 17, Date: September 18, 1998, Pages: 2395-2397 Michael Mauksch, Valentin Gogonea, Haijun Jiao, Paul von Ragué Schleyer
  10. ^ Investigation of a Putative Möbius Aromatic Hydrocarbon. The Effect of Benzannelation on Möbius [4n]Annulene Aromaticity Castro, C.; Chen, Z.; Wannere, C. S.; Jiao, H.; Karney, W. L.; Mauksch, M.; Puchta, R.; Hommes, N. J. R. v. E.; Schleyer, P. v. R. J. Am. Chem. Soc.; (Article); 2005; 127(8); 2425-2432. doi:10.1021/ja0458165
  11. ^ Expanded Porphyrin with a Split Personality: A Hückel-Möbius Aromaticity Switch Marcin Stepien , Lechosław Latos-Grazynski, Natasza Sprutta, Paulina Chwalisz, and Ludmiła Szterenberg Angew. Chem. Int. Ed. 2007, 46, 7869 –7873 doi:10.1002/anie.200700555
  12. ^ Reagents: pyrrole, benzaldehyde, boron trifluoride, subsequent oxidation with DDQ, Ph = phenyl Mes = mesityl
  13. ^ Zhu, Congqing; Ming Luo; Qin Zhu; Jun Zhu; Paul v. R. Schleyer; Judy I-Chia Wu; Xin Lu; Haiping Xia (25 February 2014). "Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums.". Nature Communications. 5: 3265. doi:10.1038/ncomms4265. PMID 24567039. 
  14. ^ "On Molecular Orbital Correlation Diagrams, the Occurrence of Möbius Systems in Cyclization Reactions, and Factors Controlling Ground and Excited State Reactions. I," Zimmerman, H. E. J. Am. Chem. Soc., 1966, 88, 1564-1565
  15. ^ "On Molecular Orbital Correlation Diagrams, Möbius Systems, and Factors Controlling Ground and Excited State Reactions. II," Zimmerman, H. E. J. Am. Chem. Soc., 1966, 88, 1566-1567