The conventional view that the σCC and σCH bonds in alkanes and unsaturated hydrocarbons are so highly localized that their non-steric interactions are negligible is scrutinized by the block-localized wavefunction (BLW) method. Even molecules considered conventionally to be “strain free” and “unperturbed” have surprisingly large and quite significant total σ-BLW-delocalization energies (DEs) due to their geminal and vicinal hyperconjugative interactions. Thus, the computed BLW-DEs (in kcal mol−1) for the antiperiplanar conformations of the n-alkanes (CNH2N+2, N = 1-10) range from 11.6 for ethane to 82.2 for n-decane and are 50.9 for cyclohexane and 91.0 for adamantane. Although σ-electron delocalization in unsaturated hydrocarbons usually is ignored, the σ-BLW-DEs (in kcal mol−1) are substantial, as exemplified by D2h ethylene (9.0), triplet D2d ethylene (16.4), allene (19.3), butadiene (19.0), hexatriene (28.3), benzene (28.1), and cyclobutadiene (21.1). While each individual geminal and vicinal hyperconjugative interaction between hydrocarbon σ-bonding and σ-antibonding orbitals tends to be smaller than an individual π conjugative interaction (e.g., 10.2 kcal mol−1 in anti-1,3-butadiene, the presence of many σ-hyperconjugative interactions (e.g., a total of 12 in anti-1,3-butadiene, see text), result in substantial total σ-stabilization energies (e.g., 19.0 kcal mol−1 for butadiene), which may surpass those from the π interactions. Although large in magnitude, σ-electron delocalization energies often are obscured by cancellation when two hydrocarbons are compared. Rather than being strain-free, cyclohexane, adamantane, and diamantane suffer from their increasing number of intramolecular 1,4-C…C repulsions resulting in elongated C–C bond lengths and reduced σ-hyperconjugation, compared to the (skew-free) antiperiplanar n-alkane conformers. Instead of being inconsequential, σ-bond interactions are important and merit consideration.
Block localized wavefunction Conjugation Electron delocalization Hauche interactions Hyperconjugation
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This work was supported by the US National Science Foundation grant CHE-105-5310 (YM), CHE-105-7466 (PvRS).
1.Department of ChemistryUniversity of GeorgiaAthensUSA
2.Department of Chemistry, College of Chemistry and Chemical Engineering, the State Key Laboratory for Physical Chemistry of Solid States, Center for Theoretical ChemistryXiamen UniversityXiamenPeople’s Republic of China
3.Department of ChemistryWestern Michigan UniversityKalamazooUSA