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Stabilizing influence of silicon substitution on dibenzene and its isomers

  • Arghadip Koner
  • Narayanasami SathyamurthyEmail author
Regular Article
  • 70 Downloads

Abstract

The stabilizing effect of silicon substitution on sixteen different isomers of dibenzene \((\hbox {C}_{{12}}\hbox {H}_{12})\) has been investigated using second-order Møller-Plesset perturbation (MP2) theory and the cc-pVDZ basis set. While the most stable isomers of \(\hbox {Si}_{{12}}\hbox {H}_{12 }\) have only Si–Si bonds, some of the stable isomers have isolated \(\hbox {Si}{=}\hbox {Si}\) bonds and may be amenable to experimental observation. Vibrational frequencies were calculated for the optimized geometries at the Hartree-Fock level of theory to ensure that they corresponded to true minima on the potential energy landscape. Natural bonding orbital analysis confirms the existence of isolated \(\hbox {Si}{=}\hbox {Si}\) double bonds in some of the isomers. Dipole moment values were determined to check for the presence of centre of symmetry in certain geometries.

Graphical Abstract

Ab initio calculations suggest that silicon analogs of several isomers of unstable dibenzene moiety are stable. While the most stable isomers of \(\hbox {Si}_{{12}}\hbox {H}_{{12}}\) have all tetrahedral silicon atoms, some of the stable isomers do contain \(\hbox {Si}{=}\hbox {Si}\) bonds, suggesting that they may be amenable to experimental observation.

Keywords

\(\hbox {Si}_{{12}}\hbox {H}_{12 }\) hexasilabenzene dimer ab initio calculations stabilization by silicon substitution 

Notes

Acknowledgements

We are grateful to Professor Roald Hoffmann for raising the question of the relative stability of the isomers of hexasilabenzene dimer and guiding us through the project. N. Sathyamurthy is an Honorary Professor at the Jawaharlal Nehru Centre for Advanced Scientific Research, Bengaluru.

Supplementary material

12039_2018_1576_MOESM1_ESM.pdf (313 kb)
Supplementary material 1 (pdf 312 KB)

References

  1. 1.
    Jose D and Datta A 2012 Understanding of the buckling distortions in silicene J. Phys. Chem. C 116 24639CrossRefGoogle Scholar
  2. 2.
    Jose D and Datta A 2014 Structures and chemical properties of silicene: Unlike graphene Acc. Chem. Res. 47 593CrossRefGoogle Scholar
  3. 3.
    Mahapatra S 2009 Excited electronic states and nonadiabatic effects in contemporary chemical dynamics Acc. Chem. Res. 42 1004CrossRefGoogle Scholar
  4. 4.
    Sinnokrot M O and Sherrill C D 2004 Highly accurate coupled cluster potential energy curves for the benzene dimer: Sandwich, T-shaped and parallel-displaced con-figurations J. Phys. Chem. A 108 10200CrossRefGoogle Scholar
  5. 5.
    Arunan E and Gutowsky H S 1993 The rotational spectrum, structure and dynamics of a benzene dimer J. Chem. Phys. 98 4294CrossRefGoogle Scholar
  6. 6.
    Rogachev A Y, Wen X-V and Hoffmann R 2012 Jailbreaking benzene dimers J. Am. Chem. Soc. 134 8062CrossRefGoogle Scholar
  7. 7.
    Equbal A, Srinivasan S and Sathyamurthy N 2017 Stabilisation of the [6]-prismane structure by silicon substitution J. Chem. Sci. 129 911CrossRefGoogle Scholar
  8. 8.
    Priyakumar U D and Sastry G N 2002 Theoretical study of silabenzene and its valence isomers Organometallics 21 1493CrossRefGoogle Scholar
  9. 9.
    Priyakumar U D, Saravanan D and Sastry G N 2002 Isomers of disilabenzene (\(\text{ C }_{{4}}\text{ Si }_{{2}}\text{ H }_{6}\)): A computational study Organometallics 21 4823CrossRefGoogle Scholar
  10. 10.
    Manjula Dhevi D, Priyakumar U D and Sastry G N 2003 Silaaromaticity in polycyclic systems: A computational study J. Org. Chem. 68 1168CrossRefGoogle Scholar
  11. 11.
    Schriver G W and Gerson D J 1990 Energies and isomerization of \((\text{ CH })_{12}\) hydrocarbons J. Am. Chem. Soc. 112 4723CrossRefGoogle Scholar
  12. 12.
    Frisch M J et al. 2010 Gaussian 09, Revision C.01, Gaussian Inc., Wallingford, CTGoogle Scholar

Copyright information

© Indian Academy of Sciences 2019

Authors and Affiliations

  1. 1.Indian Institute of Science Education and Research MohaliSAS Nagar, ManauliIndia
  2. 2.Jawaharlal Nehru Centre for Advanced Scientific ResearchJakkur, BengaluruIndia

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