A single theoretical descriptor for the bond-dissociation energy of substituted phenols
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| 008 | 210128e20150101xx s 000 0 eng | ||
| 024 | 7 | 0 | |a 10.1007/s00894-015-2572-x |2 doi |
| 035 | |a (NATIONALLICENCE)springer-10.1007/s00894-015-2572-x | ||
| 245 | 0 | 2 | |a A single theoretical descriptor for the bond-dissociation energy of substituted phenols |h [Elektronische Daten] |c [Carolina Aliaga, Iriux Almodovar, Marcos Rezende] |
| 520 | 3 | |a 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 | |
| 540 | |a Springer-Verlag Berlin Heidelberg, 2015 | ||
| 690 | 7 | |a Quantitative structure-property relationship |2 nationallicence | |
| 690 | 7 | |a Bond-dissociation energy of phenols |2 nationallicence | |
| 690 | 7 | |a Phenoxyl radicals |2 nationallicence | |
| 690 | 7 | |a Hydrogen abstraction |2 nationallicence | |
| 690 | 7 | |a DFT-based reactivity indices |2 nationallicence | |
| 700 | 1 | |a Aliaga |D Carolina |u Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile |4 aut | |
| 700 | 1 | |a Almodovar |D Iriux |u Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile |4 aut | |
| 700 | 1 | |a Rezende |D Marcos |u Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile |4 aut | |
| 773 | 0 | |t Journal of Molecular Modeling |d Springer Berlin Heidelberg |g 21/1(2015-01-01), 1-10 |x 1610-2940 |q 21:1<1 |1 2015 |2 21 |o 894 | |
| 856 | 4 | 0 | |u https://doi.org/10.1007/s00894-015-2572-x |q text/html |z Onlinezugriff via DOI |
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 900 | 7 | |a Metadata rights reserved |b Springer special CC-BY-NC licence |2 nationallicence | |
| 908 | |D 1 |a research-article |2 jats | ||
| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-springer | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1007/s00894-015-2572-x |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Aliaga |D Carolina |u Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Almodovar |D Iriux |u Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Rezende |D Marcos |u Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40 Correo 33, Santiago, Chile |4 aut | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Journal of Molecular Modeling |d Springer Berlin Heidelberg |g 21/1(2015-01-01), 1-10 |x 1610-2940 |q 21:1<1 |1 2015 |2 21 |o 894 | ||