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Comput Theor Chem 964, 2011, 329 330 .pdf

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Computational and Theoretical Chemistry 964 (2011) 329–330

Contents lists available at ScienceDirect

Computational and Theoretical Chemistry
journal homepage: www.elsevier.com/locate/comptc

Computational note

Computational note on a G4 theoretical study of the small-ring geminanes
tricyclo[,4]heptane, tetracyclo[,4.01,5]octane, and
Sierra Rayne a,⇑, Kaya Forest b

Ecologica Research, Kelowna, British Columbia V1Y 1R9, Canada
Department of Chemistry, Okanagan College, Penticton, British Columbia V2A 8E1, Canada

a r t i c l e

i n f o

a b s t r a c t

Article history:
Received 31 December 2010
Received in revised form 6 January 2011
Accepted 6 January 2011
Available online 13 January 2011

Ó 2011 Elsevier B.V. All rights reserved.

Small-ring geminanes
Inverted carbon atoms
G4 composite method
Enthalpy of formation

The small-ring geminanes are of interest due to the potential
presence of inverted carbon atoms where all substituents lie in
one hemisphere [1]. Very few molecules having carbon atoms with
such distorted configurations are known. To date, cyclobutadiene
and small-ring propellanes are the only proven examples. In prior
work using molecular mechanics (MM2), Hartree–Fock, density
functional (B3LYP), and second order Moller–Plesset perturbation
(MP2) levels of theory, Dodziuk et al. [2,3] have shown that tricyclo[,4]heptane (1), tetracyclo[,4.01,5]octane (2), and
tetracyclo[3.2.12,4.02,5]nonane (3) are stationary points on their
respective energy hypersurfaces.

Table 1

Estimated gas phase (298.15 K, 1 atm) enthalpies of formation (Df HðgÞ ) for tricyclo[,4 ]heptane (1), tetracyclo[,4.01,5]octane (2), and tetracyclo[3.2.12,4.02,5]nonane (3) at the G4 level of theory. Values are in kJ/mol.




Df HðgÞ






Current study.
From Ref. [2].
Atomization energy approach as described in Ref. [6].
Atomization energy approach as described in Refs. [7,8].


In the current study, we have conducted high-level gas phase
(298.15 K, 1 atm) Gaussian-4 (G4) [4] composite method calculations on these compounds using Gaussian 09 (G09) [5] and confirm
that the molecules represent energy minima absent imaginary frequencies (G09 archive entries provided in the Supplementary

⇑ Corresponding author. Tel.: +1 250 487 0166.
E-mail address: rayne.sierra@gmail.com (S. Rayne).
2210-271X/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.

Materials). The G4 estimated bond lengths and angles for 1–3 are
in excellent agreement with those previously obtained using the
MP2/6-31G(d,p), MP2/6-311++G(d,p), and B3LYP/6-31G(d,p)
methods [3] (Tables S1–S6). Applying the atomization energy approaches given in Refs. [6–8], respectively, yields the G4 estimated

gas phase (298.15 K, 1 atm) enthalpies of formation ðDf HðgÞ Þ given

in Table 1. The G4 Df HðgÞ are in reasonable agreement with the earlier MM2 predictions [2], and indicate these compounds are
highly-strained members of their corresponding molecular homolog groups (Table S7).

Author's personal copy


S. Rayne, K. Forest / Computational and Theoretical Chemistry 964 (2011) 329–330



This work was made possible by the facilities of the Western
Canada Research Grid (WestGrid: project 100185), the Shared
Hierarchical Academic Research Computing Network (SHARCNET:
project sn4612), and Compute/Calcul Canada. We thank an anonymous reviewer for constructive comments that improved the quality of the manuscript.

[1] H. Dodziuk, Strained Hydrocarbons: Beyond the van’t Hoff and Le Bel
Hypothesis, Wiley-VCH, 2009.
[2] H. Dodziuk, Tetrahedron 44 (1988) 2951.
[3] H. Dodziuk, J. Leszczynski, K. Jackowski, J. Org. Chem. 64 (1999) 6177.
[4] L.A. Curtiss, P.C. Redfern, K. Raghavachari, J. Chem. Phys. 126 (2007) 84108.
[5] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, et al., Gaussian 09, Revision
A.02, Gaussian, Inc., Wallingford, CT, USA, 2009.
[6] M. Saeys, M. Reyniers, G. Marin, V. Van Speybroeck, M. Waroquier, J. Phys.
Chem. A 107 (2003).
[7] A. Nicolaides, A. Rauk, M.N. Glukhovtsev, L. Radom, J. Phys. Chem. 100 (1996)
[8] R. Notario, O. Castano, J.L.M. Abboud, R. Gomperts, L.M. Frutos, R. Palmeiro, J.
Org. Chem. 64 (1999) 9011.

Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.comptc.2011.01.015.

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