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Möbius versus Hückel
The Möbius aromatic trans-C9H9+ cation.

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 nodal plane of the orbitals, viewed as a ribbon, is a Möbius strip, rather than a cylinder, hence the name. The pattern of orbital energies is given by a rotated Frost circle (with the edge of the polygon on the bottom instead of a vertex), so systems with 4n electrons are aromatic, while those with 4n + 2 electrons are anti-aromatic/non-aromatic. Due to incrementally twisted nature of the orbitals of a Möbius aromatic system, stable Möbius aromatic molecules need to contain at least 8 electrons, although 4 electron Möbius aromatic transition states are well known in the context of the Dewar-Zimmerman framework for pericyclic reactions. Möbius molecular systems were considered in 1964 by Edgar Heilbronner by application of the Hückel method,[3] but the first such isolable compound was not synthesized until 2003 by the group of Rainer Herges.[4] However, the fleeting trans-C9H9+ cation, one conformation of which is shown on the right, was proposed to be Möbius aromatic in 1998 based on computational and experimental data.


Contents

Hückel-Möbius aromaticityEdit

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]

 

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]

 

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]

 
Computed structure of trans-C9H9+, 2, illustrating the twisted nature of the ring, allowing incremental rotation of the orientation of p atomic orbitals around the ring: tracing the p orbitals all the way around the ring results in a phase inversion relative to the starting p orbital. The plane of the carbon skeleton (i.e., the nodal plane of the p orbitals) forms a Möbius strip.
 

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]

 

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 statesEdit

In contrast to the rarity of Möbius aromatic ground state molecular systems, there are many examples of pericyclic transition states that exihibit Möbius aromaticity. The classification of a pericyclic transition state as either Möbius or Hückel topology determines whether 4N or 4N + 2 electrons are required to make the transition state aromatic or antiaromatic, and therefore, allowed or forbidden, respectively. Based on the energy level diagrams derived from Hückel MO theory, (4N + 2)-electron Hückel and (4N)-electron Möbius transition states are aromatic and allowed, while (4N + 2)-electron Möbius and (4N)-electron Hückel transition states are antiaromatic and forbidden. This is the basic premise of the Möbius-Hückel concept.[14][15]

Derivation of Hückel MO theory energy levels for Möbius topologyEdit

From the figure above, it can also be seen that the interaction between two consecutive   AOs is attenuated by the incremental twisting between orbitals by  , where   is the angle of twisting between consecutive orbitals, compared to the usual Hückel system. For this reason resonance integral   is given by

 ,

where   is the standard Hückel resonance integral value (with completely parallel orbitals). Nevertheless, after going all the way around, the Nth and 1st orbitals are almost completely out of phase. (If the twisting were to continue after the  th orbital, the  st orbital would be exactly phase-inverted compared to the 1st orbital). For this reason, in the Hückel matrix the resonance integral between carbon   and   is  .
For the generic   carbon Möbius system, the Hamiltonian matrix   is:

 .

Eigenvalues for this matrix can now be found, which correspond to the energy levels of the Möbius system. Since   is a   matrix, we will have   eigenvalues   and   MOs. Defining the variable

 ,

we have:

 .

To find nontrivial solutions to this equation, we set the determinant of this matrix to zero to obtain

 .

Hence, we find the energy levels for a cyclic system with Möbius topology,

 .

In contrast, recall the energy levels for a cyclic system with Hückel topology,

 .

See alsoEdit

ReferencesEdit

  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. Bibcode:2014NatCo...5E3265Z. 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