caa a22 4500 605488061 CHVBK 20210128100453.0 cr unu---uuuuu 210128e20150801xx s 000 0 eng 10.1007/s00214-015-1706-7 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1706-7 On the nature of halogen bonded complexes between carbonyl bases and chlorotrifluoromethane [Elektronische Daten] [Wiktor Zierkiewicz, Dariusz Bieńko, Danuta Michalska, Thérèse Zeegers-Huyskens] The structures and intermolecular interactions in the halogen bonded complexes of six carbonyl bases with chlorotrifluoromethane have been studied by ab initio MP2 and CCSD(T) as well as density functional methods: B3LYP, B3LYP-D3 and wB97XD. The CCSD(T)/aug-cc-pVTZ calculated interaction energies of these complexes range between −1.22 and −2.62kcalmol−1. The interaction energies are related to the ionization potential and proton affinity of the carbonyl bases. The intermolecular interaction results in a contraction of the C-Cl bond and an elongation of the C-F bonds accompanied by a relevant frequency shift of the corresponding stretching vibrations. The origin of the variation of the C-Cl and C-F bond lengths is discussed on the basis of an NBO analysis. It is suggested that the formation of these complexes can be considered as a two-step mechanism, involving the intermolecular charge transfer from the lone-pair orbitals on the oxygen atom to the antibonding σ*(C-Cl) orbital followed by a decrease of the intramolecular charge transfer from the lone-pair orbitals on the fluorine atoms to the antibonding σ*(C-Cl) orbital. A symmetry-adapted perturbation theory (SAPT) decomposition of the interaction energies has been performed. The Author(s), 2015 Halogen bond nationallicence Carbonyl bases nationallicence DFT nationallicence MP2 nationallicence CCSD(T) nationallicence Zierkiewicz Wiktor Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370, Wrocław, Poland aut Bieńko Dariusz Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370, Wrocław, Poland aut Michalska Danuta Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370, Wrocław, Poland aut Zeegers-Huyskens Thérèse Department of Chemistry, University of Leuven, 200F Celestijnenlaan, 3001, Heverlee, Belgium aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/8(2015-08-01), 1-13 1432-881X 134:8<1 2015 134 214 https://doi.org/10.1007/s00214-015-1706-7 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1706-7 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Zierkiewicz Wiktor Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370, Wrocław, Poland aut NATIONALLICENCE 700 1- Bieńko Dariusz Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370, Wrocław, Poland aut NATIONALLICENCE 700 1- Michalska Danuta Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370, Wrocław, Poland aut NATIONALLICENCE 700 1- Zeegers-Huyskens Thérèse Department of Chemistry, University of Leuven, 200F Celestijnenlaan, 3001, Heverlee, Belgium aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/8(2015-08-01), 1-13 1432-881X 134:8<1 2015 134 214