Clark T (2019)
Publication Type: Journal article
Publication year: 2019
Book Volume: 123
Pages Range: 3326-3333
Journal Issue: 15
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.
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.
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