On the Stability of Cis‐ and Trans‐2‐Butene Isomers. An Insight Based on the FAMSEC, IQA, and ETS‐NOCV Schemes. Issue 32 (12th October 2016)

• Record Type: Journal Article
• Authors: Cukrowski, Ignacy; Sagan, Filip; Mitoraj, Mariusz Paweł
• Is Part Of: Journal of computational chemistry. Volume 37:Issue 32(2016)
• Page Start: 2783
• Page End: 2798
• Publication Date: 2016-10-12
• Subjects: 2‐butene -- FAMSEC -- ETS‐NOCV -- IQA -- computational chemistry -- intramolecular H–H interactions; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.24504
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract : In the present account, the real space fragment attributed molecular system energy change (FAMSEC) approach, interacting quantum atoms energy decomposition scheme as well as molecular orbitals based the extended transition state scheme coupled with natural orbitals for chemical valence (ETS‐NOCV) have been, for the first time, successfully used to delineate factors of importance for stability of the 2‐butene conformers ( cis ‐eq, cis ‐TS, trans ‐eq, trans ‐TS). Our results demonstrate that atoms of the controversial H–H contact in cis ‐eq (i) are involved in attractive interaction dominated by the exchange‐correlation term, (ii) are weekly stabilized, (iii) show trends in several descriptors found in other typical H‐bonds, and (iv) are part of most stabilized CH–HC fragment ( loc ‐FAMSEC = −3.6 kcal/mol) with most favourably changed intrafragment interactions on trans ‐eq→ cis ‐eq. Moreover, lower stability of cis ‐eq vs. trans ‐eq is linked with the entire HCCH (ethylenic) fragment which destabilized cis ‐eq ( mol ‐FAMSEC, +3.9 kcal/mol) the most. Although the H–H contact can be linked with smaller, relative to trans ‐, rotational energy barrier in cis ‐2‐butene, we have proven that to rationalize this phenomenon one must account for changes in interactions between various fragments that constitute the entire molecule. Importantly, we discovered a number of comparable trends in fundamental properties of equivalent molecular fragments on a methyl group rotation; for example, interaction between BP‐free H‐atoms in trans ‐eq (involving CH bonds of the methyl and ethylenic units) and BP‐linked H‐atoms in cis ‐eq. Clearly, rotational energy barrier cannot be entirely (i) rationalized by the properties of or (ii) attributed to the H–H contact in cis ‐eq. © 2016 Wiley Periodicals, Inc. Abstract : To describe 2‐butene isomers, real space Fragment Attributed Molecular System Energy Change and Extended Transition State coupled with the Natural Orbitals for Chemical Valence methods are applied for the first time. HH in cis ‐eq and cis ‐TS (i) is stabilized and strain‐free, (ii) diatomic interaction has several features typical for a classical H‐bond, and (iii) can be linked with smaller, relative to trans ‐2‐butene, rotational energy barrier. E ( cis ) > E ( trans ) is linked with the HCCH fragment.