Journal of Molecular Modeling

, Volume 19, Issue 6, pp 2549–2557 | Cite as

Natural bond orbital, nuclear magnetic resonance analysis and hybrid-density functional theory study of σ-aromaticity in Al2F6, Al2Cl6, Al2Br6 and Al2I6

  • Davood Nori-Shargh
  • Hooriye Yahyaei
  • Seiedeh Negar Mousavi
  • Akram Maasoomi
  • Hakan Kayi
Original Paper

Abstract

Natural bond orbital (NBO), nuclear magnetic resonance (NMR) analysis and hybrid-density functional theory based method (B3LYP/Def2-TZVPP) were used to investigate the correlation between the nucleus-independent chemical shifts [NICS, as an aromaticity criterion], σAl(1)-X2(b)σ*Al(3)-X4(b) electron delocalizations and the dissociation energies of Al2F6, Al2Cl6, Al2Br6 and Al2I6 to 2AlX3 (X = F, Cl, Br, I). The results obtained showed that the dissociation energies of Al2F6, Al2Cl6, Al2Br6 and Al2I6 decrease from Al2F6 to Al2I6. Like aromatic molecules, these compounds have relatively significant negative NICSiso(0) values. Clearly, based on magnetic criteria, they exhibit aromatic character and make it possible to consider them as σ-delocalized aromatic species, such as Möbius σ-aromatic species. The σ-aromatic character which is demonstrated by their NICSiso(0) values decreases from Al2F6 to Al2I6. The NICSiso values are dominated by the in-plane σ22 (i.e., σyy, the plane containing halogen atoms bridged) chemical shift components. The increase of the NICSiso values explains significantly the decrease of the corresponding dissociation energies of Al2F6, Al2Cl6, Al2Br6 and Al2I6. Importantly, the NBO results suggest that in these compounds the dissociation energies are controlled by the stabilization energies associated with σAl(1)-X2(b)σ*Al(3)-X4(b) electron delocalizations. The decrease of the stabilization energies associated with σAl(1)-X2(b)σ*Al(3)-X4(b) electron delocalizations is in accordance with the variation of the calculated NICSiso values. The correlations between the dissociation energies of Al2F6, Al2Cl6, Al2Br6 and Al2I6, σAl(1)-X2(b)σ*Al(3)-X4(b) electron delocalizations, natural atomic orbitals (NAOs) and NICSiso values have been investigated.

Keywords

Hybrid-DFT calculations Al2F6 Al2Cl6 Al2Br6 Al2I6 AM1* NBO NICS 

References

  1. 1.
    Wells F (1984) Structural inorganic chemistry. Clarendon, Oxford Google Scholar
  2. 2.
    Greenwood NN, Earnshaw A (1984) Chemistry of the elements. Pergamon, OxfordGoogle Scholar
  3. 3.
    Shriver DF, Atkins PW, Langford CH (1992) Inorganic chemistry. Oxford University Press, OxfordGoogle Scholar
  4. 4.
    Olah GA, Meyer MW (1963) In: Friedelcrafts and related reactions. Olah GA (Ed.), Interscience,New york 1: 623 765Google Scholar
  5. 5.
    Aarset K, Shen Q, Thomassen H, Richardson AD, Hedberg K (1999) Molecular structure of the aluminum halides, Al2Cl6, AlCl3, Al2Br6, AlBr3, and AlI3, obtained by gas-phase electron-diffraction and ab initio molecular orbital calculations. J Phys Chem A 103:1644–1652. doi:10.1021/jp9842042, and references thereinCrossRefGoogle Scholar
  6. 6.
    Curtiss LA (1978) Molecular orbital studies of Al2F6 and Al2Cl6 using a minimal basis set. Int J Quantum Chem 14:709–715. doi:10.1002/qua.560140602 CrossRefGoogle Scholar
  7. 7.
    Williams SD, Harper W, Mamantov G, Tortorelli LJ, Shankle G (1996) Ab initio MO study of selected aluminum and boron chlorides and fluorides: Comparison with 11B NMR spectra of a tetrachloroborate melt. J Comput Chem 17:1696–1711. doi:10.1002/(SICI)1096-987X(19961130) CrossRefGoogle Scholar
  8. 8.
    Scholz G, Schöffel K, Jensen VR, Bache Ø, Ystenesc M (1994) Vibrational frequencies of AlF3: An ab initio MO study evaluating different methods on a tricky case. Chem Phys Lett 230:196–202. doi:10.1016/0009-2614(94)01101-X CrossRefGoogle Scholar
  9. 9.
    Göller A, Clark T (2000) σ*-aromaticity in three membered rings. J Mol Model 6:133–149. doi:10.1007/PL00010724 CrossRefGoogle Scholar
  10. 10.
    Li ZH, Moran D, Fan KN, PvR S (2005) Sigma-aromaticity and sigma-antiaromaticity in saturated inorganic rings. J Phys Chem A 109:3711–3716. doi:10.1021/jp048541o CrossRefGoogle Scholar
  11. 11.
    Wu W, Ma B, Wu JIC, PvR S, Mo Y (2009) Is cyclopropane really the sigma-aromatic paradigm? CHEM EUR J 15:9730–9736. doi:10.1002/chem.200900586 CrossRefGoogle Scholar
  12. 12.
    Havenith RWA, De Proft F, Fowler PW, Geerlings P (2005) sigma-Aromaticity in H-3(+) and Li-3(+): insights from ring-current maps. Chemical Physics Letters 407:391–396. doi:10.1016/j.cplett.2005.03.099 CrossRefGoogle Scholar
  13. 13.
    Glendening ED, Badenhoop JK, Reed AE, Carpenter JE, Bohmann JA, Morales CM, Weinhold F (2004) NBO Version 5.G. Theoretical Chemistry Institute. University of Wisconsin, MadisonGoogle Scholar
  14. 14.
    Reed AE, Curtiss LA, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem Rev 88:899–926. doi:10.1021/cr00088a005 CrossRefGoogle Scholar
  15. 15.
    Chen Z, Wannere CS, Corminboeuf C, Puchta R, PvR S (2005) Nucleus-independent chemical shifts (NICS) as an aromaticity criterion. Chem Rev 105:3842–3888. doi:10.1021/cr030088+ CrossRefGoogle Scholar
  16. 16.
    Garratt PG (1986) Aromaticity. Wiley, New YorkGoogle Scholar
  17. 17.
    Katritzky A, Barczynski P, Musumarra G, Pisano D, Szafran M (1989) Aromaticity as a quantitative concept. 1. A statistical demonstration of the orthogonality of classical and magnetic aromaticity in five- and six-membered heterocycles. J Am Chem Soc 111:7–15. doi:10.1021/ja00183a002 CrossRefGoogle Scholar
  18. 18.
    Jug K, Köster AM (1991) Aromaticity as a multi-dimentional phenomenon. J Phys Org Chem 4:163–169. doi:10.1002/poc.610040307 CrossRefGoogle Scholar
  19. 19.
    Minkin VI, Glukhovstsev MN, Simkin BY (1994) Aromaticity and Antiaromaticity. Wiley, New YorkGoogle Scholar
  20. 20.
    Schleyer PR, Jiao H (1996) What is Aromaticity? Pure & Appl Chem 68:209–218. doi:10.1351/pac199668020209 CrossRefGoogle Scholar
  21. 21.
    von Ragué Schleyer P, Maerker C, Dransfeld A, Jiao H, van Eikema Hommes NJR (1996) Nucleus-independent chemical shifts: a simple and efficient aromaticity probe. J Am Chem Soc 118:6317–6318. doi:10.1021/ja960582d CrossRefGoogle Scholar
  22. 22.
    Nyulaszi L, PvR S (1999) Hyperconjugative-aromaticity: how to make cyclopentadiene aromatic. J Am Chem Soc 121:6872–6875. doi:10.1021/ja983113f CrossRefGoogle Scholar
  23. 23.
    Heilbronner E (1964) Tetrahedron Lett 5(29):1923–1928Google Scholar
  24. 24.
    Zimmerman HE (1971) Acc Chem Res 4:272–228CrossRefGoogle Scholar
  25. 25.
    Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652. doi:10.1063/1.464913 CrossRefGoogle Scholar
  26. 26.
    Yang LW, Parr RG (1988) Development of the Colle-Salvetti conelation energy formula into a functional of the electron density. Phys Rev B 37:785–789. doi:10.1103/PhysRevB.37.785 CrossRefGoogle Scholar
  27. 27.
    Vosko SH, Wilk L, Nusair M (1980) Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis. Can J Phys 58:1200–1211. doi:10.1139/p80-159 CrossRefGoogle Scholar
  28. 28.
    Stephens PJ, Devlin FJ, Chabalowski CF, Frisch MJ (1994) Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields. J Phys Chem 98:11623–11627. doi:10.1021/j100096a001 CrossRefGoogle Scholar
  29. 29.
    Seminario JM, Politzer P (1995) An introduction to density functional theory in chemistry. In: Seminario JM (ed) Density functional theory: a tool for chemistry. Elsevier, AmsterdamGoogle Scholar
  30. 30.
    Weigend F, Ahlrichs R (2005) Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design an assessment of accuracy. Phys Chem Chem Phys 7:3297–3305. doi:10.1039/B508541A CrossRefGoogle Scholar
  31. 31.
    Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su SJ, Windus TL, Dupuis M, Montgomery JA (1993) J Comput Chem 14:1347–1363CrossRefGoogle Scholar
  32. 32.
    Clark T, Alex A, Beck B, Chandrasekhar J, Gedeck P, Horn AHC, Hutter M, Martin B, Rauhut G, Sauer W, Schindler T, Steinke T (2005) VAMP 10.0. Computer-Chemie-Centrum. Universität Erlangen-Nürnberg, ErlangenGoogle Scholar
  33. 33.
    McIver JW (1974) The structure of transition states: are they symmetric? Jr Acc Chem Res 7:72–77. doi:10.1021/ar50075a002 CrossRefGoogle Scholar
  34. 34.
    Ermer O (1975) Determination of molecular symmetries by force field calculations and evaluation of symmetric and nonsymmetric conformational transition states avoiding complete point-by-point mapping. Tetrahedron 31:1849–1854. doi:10.1016/0040-4020(75)87040-2 CrossRefGoogle Scholar
  35. 35.
    Dionne P, St-Jacques M (1987) Mechanism of the gauche conformational effect in 3-halogenated 1,5-benzodioxepins. J Am Chem Soc 109:2616–2623. doi:10.1021/ja00243a012 CrossRefGoogle Scholar
  36. 36.
    Weinhold F (2003) Rebuttal to the bickelhaupt–baerends case for steric repulsion causing the staggered conformation of ethane. Angew Chem Int Ed 42:4188–4194. doi:10.1002/anie.200351777 CrossRefGoogle Scholar
  37. 37.
    Tapu DA, Dixon DA, Roe C (2009) 13C NMR spectroscopy of “Arduengo-type” carbenes and their derivatives. Chem Rev 109:3385–3407. doi:10.1021/cr800521g CrossRefGoogle Scholar
  38. 38.
    Winget P, Horn AHC, Selçuki C, Martin B, Clark T (2003) AM1* parameters for phosphorus, sulfur and chlorine. J Mol Model 9:408–414CrossRefGoogle Scholar
  39. 39.
    Winget P, Clark T (2005) AM1* parameters for aluminum, silicon, titanium and zirconium. J Mol Model 11:439–456CrossRefGoogle Scholar
  40. 40.
    Kayi H, Clark T (2009) AM1* parameters for bromine and iodine. J Mol Model 15:295–308CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Davood Nori-Shargh
    • 1
  • Hooriye Yahyaei
    • 2
  • Seiedeh Negar Mousavi
    • 1
  • Akram Maasoomi
    • 1
  • Hakan Kayi
    • 3
    • 4
  1. 1.Department of Chemistry, Arak BranchIslamic Azad UniversityArakIran
  2. 2.Department of Chemistry, Zanjan BranchIslamic Azad UniversityZanjanIran
  3. 3.Institute for Theoretical Chemistry, Department of Chemistry and BiochemistryThe University of TexasAustinUSA
  4. 4.Department of Chemical Engineering and Applied ChemistryAtilim UniversityAnkaraTurkey

Personalised recommendations