Interaction of Radicals with σ-Holes

Journal article


Publication Details

Author(s): Clark T
Journal: Journal of Physical Chemistry A
Publication year: 2019
Volume: 123
Journal issue: 15
Pages range: 3326-3333
ISSN: 1520-5215
eISSN: 1089-5639


Abstract

The noncovalent interactions of the CH
3


, Cl

, CF
3


, and C(CH
3
)
3


radicals with CF
3
X molecules (X = Cl, Br, I) have been investigated using CCSD(T)/aug-cc-pVTZ energy calculations on MP2/aug-cc-pVTZ-optimized geometries. The electrophilic chlorine atom prefers to complex with the equatorial belt of the heavier halogen X, whereas the nucleophilic radicals CH
3


and C(CH
3
)
3


coordinate preferentially with the σ-hole of X to give C
3v
complexes. Complexation energies are generally small, ranging up to 5 kcal mol
-1
for CF
3
I with either the chlorine atom or the
t
Bu radical. Within the continuum from pure one-electron (SOMO-LUMO) to pure three-electron (SOMO-HOMO) bonds, the results can be interpreted in terms of predominantly one-electron bonds for nucleophilic radicals but closer to three-electron bonds for the chlorine atom. The trifluoromethyl radical binds very weakly via interhalogen interactions; the carbon radical center plays no role in the bonding.


FAU Authors / FAU Editors

Clark, Timothy apl. Prof. Dr.
Computer-Chemie-Centrum


How to cite

APA:
Clark, T. (2019). Interaction of Radicals with σ-Holes. Journal of Physical Chemistry A, 123(15), 3326-3333. https://dx.doi.org/10.1021/acs.jpca.9b01133

MLA:
Clark, Timothy. "Interaction of Radicals with σ-Holes." Journal of Physical Chemistry A 123.15 (2019): 3326-3333.

BibTeX: 

Last updated on 2019-06-08 at 09:07