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 on a G4 theoretical study of the small-ring geminanes
tricyclo[3.1.1.01,4]heptane, tetracyclo[126.96.36.199,4.01,5]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
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.
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 . 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[3.1.1.01,4]heptane (1), tetracyclo[188.8.131.52,4.01,5]octane (2), and
tetracyclo[3.2.12,4.02,5]nonane (3) are stationary points on their
respective energy hypersurfaces.
Estimated gas phase (298.15 K, 1 atm) enthalpies of formation (Df HðgÞ ) for tricyclo[3.1.1.01,4 ]heptane (1), tetracyclo[184.108.40.206,4.01,5]octane (2), and tetracyclo[3.2.12,4.02,5]nonane (3) at the G4 level of theory. Values are in kJ/mol.
From Ref. .
Atomization energy approach as described in Ref. .
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)  composite method calculations on these compounds using Gaussian 09 (G09)  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: firstname.lastname@example.org (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  (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 , and indicate these compounds are
highly-strained members of their corresponding molecular homolog groups (Table S7).
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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.
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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.