Correlation Effects on the Relative Stabilities of Alkanes

• Published in: Journal of the American Chemical Society Vol. 135; no. 35; pp. 13008 - 13014
• Main Authors: McKee, William C, Schleyer, Paul von Ragué
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.09.2013
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja403934s

The “alkane branching effect” denotes the fact that simple alkanes with more highly branched carbon skeletons, for example, isobutane and neopentane, are more stable than their normal isomers, for example, n-butane and n-pentane. Although n-alkanes have no branches, the “kinks” (or “protobranches”) in their chains (defined as the composite of 1,3-alkyl–alkyl interactionsincluding methine, methylene, and methyl groups as alkyl entitiespresent in most linear, cyclic, and branched alkanes, but not methane or ethane) also are associated with lower energies. Branching and protobranching stabilization energies are evaluated by isodesmic comparisons of protobranched alkanes with ethane. Accurate ab initio characterization of branching and protobranching stability requires post-self-consistent field (SCF) treatments, which account for medium range (∼1.5–3.0 Å) electron correlation. Localized molecular orbital second-order Møller–Plesset (LMO-MP2) partitioning of the correlation energies of simple alkanes into localized contributions indicates that correlation effects between electrons in 1,3-alkyl groups are largely responsible for the enhanced correlation energies and general stabilities of branched and protobranched alkanes.