Halogen bonds between 2,2,6,6-tetramethylpiperidine-N-oxyl radical and CxHyFzI species: DFT calculations of physicochemical properties and comparison with hydrogen bonded adducts.
Structural, thermodynamic, and magnetic properties of adducts between the 2,2,6,6-tetramethylpiperidine-N-oxyl radical and representative hydrogen and halogen bond donors in solution have been investigated by an integrated computational tool including hybrid density functionals and discrete-continuum solvent models. From a quantitative point of view, the computed values show a fair agreement with experiment when environmental effects are taken into the proper account. From a more general point of view, our analysis points out a number of analogies, but also some difference, between hydrogen and halogen bond, which have been interpreted in terms of the various effects tuning thermodynamic and spectroscopic parameters.
Dipartimento di Chimica, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, I-80126, Napoli, Italy. cimino@unisa.it
Paola
P
Cimino
Michele
M
Pavone
Vincenzo
V
Barone
D003198:Computer Simulation; D003497:Cyclic N-Oxides / Q000737:chemistry*; D005609:Free Radicals; D006219:Halogens / Q000737:chemistry*; D006846:Hydrocarbons, Halogenated / Q000737:chemistry*; D006860:Hydrogen Bonding; D008956:Models, Chemical; D015394:Molecular Structure; D011789:Quantum Theory
D003497:Cyclic N-Oxides; D005609:Free Radicals; D006219:Halogens; D006846:Hydrocarbons, Halogenated; C003959:TEMPO