Assessing the attractive/repulsive force balance in axial cyclohexane C-Hax ···Yax contacts A combined computational analysis in monosubstituted cyclohexanes

Assessing the attractive/repulsive force balance in axial cyclohexane C-Hax ···Yax contacts : A combined computational analysis in monosubstituted cyclohexanes

© 2016 Wiley Periodicals, Inc.

Bibliographische Detailangaben
Veröffentlicht in:Journal of computational chemistry. - 1984. - 37(2016), 30 vom: 15. Nov., Seite 2647-2658
1. Verfasser: Silva Lopez, Carlos (VerfasserIn)
Weitere Verfasser: Nieto Faza, Olalla, De Proft, Frank, Kolocouris, Antonios
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2016
Zugriff auf das übergeordnete Werk:Journal of computational chemistry
Schlagworte:Journal Article Research Support, Non-U.S. Gov't Grimme's dispersion correction NBO QTAIM Weizsäcker kinetic energy attractive forces axial cyclohexane contacts non-covalent interactions
Beschreibung
Zusammenfassung:© 2016 Wiley Periodicals, Inc.
The interactions of axial substituents in monosubstituted cyclohexane rings are studied in this work using an array of different computational techniques. Additionally, the anomalous axial preference for some bulky substituents is related to stabilizing dispersion interactions. We find that the C-Hax ···Yax contacts for various substituents with distances ranging from 2 to ∼5 Å may include attractive dispersion forces that can affect the conformational equilibrium; these forces co-exist with Pauli repulsive forces effected by Yax group due to van der Waals sphere penetration. At distances between 2 and 3 Å stabilizing electron transfer interactions were calculated and the combination of natural bond orbital and QTAIM analysis showed that, in certain cases, Yax  = t Bu, Cax -O or Cax  = O or Sax  = O or Cax  = S this interaction can be characterized as an improper H-bond. DFT-D3 and non-covalent interactions calculations (NCIs) in cyclohexane derivatives with Yax  = SiOR3 including HYax ···Hcy surfaces at distances ranging between 4 and 6 Å suggest that dispersion has a clear effect on the experimentally observed stabilization of the axial conformer. NCIs computed from the reduced density gradient help to visually identify and analyze these interactions. © 2016 Wiley Periodicals, Inc
Beschreibung:Date Completed 19.07.2018
Date Revised 19.07.2018
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:1096-987X
DOI:10.1002/jcc.24496