Theoretical description of halogen bonding – an insight based on the natural orbitals for chemical valence combined with the extended-transition-state method (ETS-NOCV)

摘要

In the present study we have characterized the halogen bonding in selected molecules H3N–ICF3 (>1-NH>3), (PH3)2C–ICF3 (>1-CPH>3), C3H7Br–(IN2H2C3)2C6H4 (>2-Br), H2–(IN₂H₂C₃)₂C₆H₄ (>2-H_>2>) and Cl–(IC₆F₅)₂C₇H₁₀N₂O₅ (>3-Cl), containing from one halogen bond (>1-NH_>3, >1-CPH_>3) up to four connections in >3-Cl (the two Cl–HN and two Cl–I), based on recently proposed ETS-NOCV analysis. It was found based on the NOCV-deformation density components that the halogen bonding C–X^>…B (X-halogen atom, B-Lewis base), contains a large degree of covalent contribution (the charge transfer to X^>…B inter-atomic region) supported further by the electron donation from base atom B to the empty σ*(C–X) orbital. Such charge transfers can be of similar importance compared to the electrostatic stabilization. Further, the covalent part of halogen bonding is due to the presence of σ-hole at outer part of halogen atom (X). ETS-NOCV approach allowed to visualize formation of the σ-hole at iodine atom of CF₃I molecule. It has also been demonstrated that strongly electrophilic halogen bond donor, [C₆H₄(C₃H₂N₂I)₂][OTf]₂, can activate chemically inert isopropyl bromide (>2-Br) moiety via formation of Br–I bonding and bind the hydrogen molecule (>2-H_>2). Finally, ETS-NOCV analysis performed for >3-Cl leads to the conclusion that, in terms of the orbital-interaction component, the strength of halogen (Cl–I) bond is roughly three times more important than the hydrogen bonding (Cl–HN).>FigureETS-NOCV reprezentation of σ-hole at iodine together with the molecular electrostatic potential picture