Preparation and Reactivity of [D3d]‐Octahedrane: The Most Stable (CH)12 Hydrocarbon

Meijere, Armin de; Lee, Chi−Hung; Кузнецов, М. А.; Gusev, Dmitriy V.; Kozhushkov, Sergei I.; Fokin, Andrey A.; Schreiner, Peter R.

doi:10.1002/chem.200500472

Cited by 32 publications

(36 citation statements)

References 54 publications

(60 reference statements)

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“…There have been a number of studies32, 44–49 on isomers of the C 12 H 12 hydrocarbon, which was all triggered by a report of the preparation and reactivity of D 3d ‐octahedrane 44, 45. This latter compound was claimed to be the most stable C 12 H 12 isomer despite a considerable strain,47 but this was later shown to be incorrect: dimethylnaphthalenes were even more stable 46.…”

Section: Resultsmentioning

confidence: 99%

Inter‐ and intramolecular dispersion interactions

2010

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Abstract:We have investigated the performance of a variety of density functional methods for weak intra-and intermolecular dispersion interactions. Grimme's empirical dispersion correction method is shown to give a good description for these interactions and helps to improve the description of water-hexamer isomers, noble-gas dimers, hydrocarbon C 12 H 12 isomers, branching energy of linear versus branched octane, dissociation of the covalently bound anthracene dimer, and stacking within the adenine dimer. However, the dispersion correction does not correct all shortcomings of the different density functionals, which leads to sizeable differences compared to ab initio CCSD(T) and experimental reference data. The only exception is shown to be our recently presented SSB-D functional that works well for all systems studied here.

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Section: Resultsmentioning

confidence: 99%

Inter‐ and intramolecular dispersion interactions

2010

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“…Despite its strain, octahedrane ( 6 , Fig. ) also is the most thermodynamically stable (CH) 12 hydrocarbon …”

Section: Introductionmentioning

confidence: 99%

Heats of formation of platonic hydrocarbon cages by means of high‐level thermochemical procedures

2015

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Hydrocarbon cages are key reference materials for the validation and parameterization of computationally cost-effective procedures such as density functional theory (DFT), semiempirical molecular orbital theory, and molecular mechanics. We obtain accurate total atomization energies (TAEs) and heats of formation (Δf H°298) for platonic and prismatic hydrocarbon cages by means of the Wn-F12 explicitly correlated thermochemical protocols. We consider the following kinetically stable (CH)n polycyclic hydrocarbon cages: (i) platonic hydrocarbons (tetrahedrane, cubane, and dodecahedrane), (ii) prismatic hydrocarbons (triprismane, cubane, and pentaprismane), and (iii) one truncated tetrahedrane (octahedrane). Our best theoretical heat of formation for cubane (144.8 kcal mol(-1)) suggests that the experimental value adopted by the NIST thermochemical database (142.7 ± 1.2 kcal mol(-1)) should be revised upwards by ∼2 kcal mol(-1). Our best heat of formation for dodecahedrane (20.2 kcal mol(-1)) suggests that the semiexperimental value (22.4 ± 1 kcal mol(-1)) should be revised downward by ∼2 kcal mol(-1). We use our benchmark Wn-F12 TAEs to evaluate the performance of a variety of computationally less demanding composite thermochemical procedures. These include the Gaussian-n (Gn) and the complete basis set (CBS) methods. The CBS-QB3 and CBS-APNO procedures show relatively poor performance with root-mean-squared deviations (RMSDs) of 4.2 and 2.5 kcal mol(-1), respectively. The best performers of the Gn procedures are G4 and G3(MP2)B3 (RMSD = 0.5 and 0.6 kcal mol(-1), respectively), while the worst performers are G3 and G4(MP2)-6X (RMSD = 2.1 and 2.9 kcal mol(-1), respectively). Isodesmic and even homodesmotic reactions involving these species are surprisingly challenging targets for DFT computations.

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“…[15] At first glance, it is rather surprising that a highly strained hydrocarbon such as octahedrane (1) is the most stable (CH) 12 structure. [18] Indeed, common DFT approaches such as BLYP and B3LYP favor 2 or 3 (Scheme 1), while high-level CCSD(T)/cc-pVDZ// MP2/aug-cc-pVDZ computations strongly favor 1 (by 14.3 and 25.0 kcal mol À1 , respectively). Systematic studies on larger hydrocarbons including structures with strained rings and unsaturation revealed also that the errors increase with the size of the system and that computations on structures with only single bonds are more error-prone than others.…”

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confidence: 99%