caa a22 4500 605510814 CHVBK 20210128100648.0 cr unu---uuuuu 210128e20150101xx s 000 0 eng 10.1007/s00894-015-2572-x doi (NATIONALLICENCE)springer-10.1007/s00894-015-2572-x A single theoretical descriptor for the bond-dissociation energy of substituted phenols [Elektronische Daten] [Carolina Aliaga, Iriux Almodovar, Marcos Rezende] Relative to the corresponding value of phenol, the bond-dissociation energies (BDE) of substituted phenols correlate well with a single descriptor: the Mulliken charge on the oxygen atom of the phenoxyl radical. However, the correlation fails for phenols ortho-substituted with polar groups. Internal reaction coordinates (IRC) for the model reaction of hydrogen abstraction by the hydroperoxyl radical from various 2- and 4-substituted phenols were calculated in order to investigate the role of intra-molecular hydrogen bonds and steric effects on the process. Calculations yielded theoretical values in good agreement with experimental ΔBDE values. The hydrogen-abstraction process was further analyzed in terms of density functional theory (DFT)-based reactivity indices such as local electrophilicity, the Fukui function for nucleophilic attack, and dual descriptor values of the phenolic hydroxyl oxygen along the IRC. Graphical abstract Bond-dissociation energies (BDEs) of phenols correlate with a single descriptor. Local electrophilicities, Fukui functions and dual descriptors were used to analyze a model ArO···H···OOH process Springer-Verlag Berlin Heidelberg, 2015 Quantitative structure-property relationship nationallicence Bond-dissociation energy of phenols nationallicence Phenoxyl radicals nationallicence Hydrogen abstraction nationallicence DFT-based reactivity indices nationallicence Aliaga Carolina Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile aut Almodovar Iriux Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile aut Rezende Marcos Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/1(2015-01-01), 1-10 1610-2940 21:1<1 2015 21 894 https://doi.org/10.1007/s00894-015-2572-x text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2572-x text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Aliaga Carolina Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile aut NATIONALLICENCE 700 1- Almodovar Iriux Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile aut NATIONALLICENCE 700 1- Rezende Marcos Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/1(2015-01-01), 1-10 1610-2940 21:1<1 2015 21 894