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.
Cimino
Paola
P
Dipartimento di Chimica, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, I-80126, Napoli, Italy. cimino@unisa.it
Pavone
Michele
M
Barone
Vincenzo
V
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