Dedicated to memory of Professor Marvin Charton from Pratt Institute (Brooklyn, New York), the prominent scientist working in the field of physical organic chemistry with a particular contribution to problems of substituent effects.
Complexes of 4-substituted phenolates with HF and HCN: Energy decomposition and electronic structure analyses of hydrogen bonding†
Article first published online: 23 NOV 2012
Copyright © 2012 Wiley Periodicals, Inc.
Journal of Computational Chemistry
Volume 34, Issue 8, pages 696–705, 30 March 2013
How to Cite
Szatyłowicz, H., Krygowski, T. M., Fonseca Guerra, C. and Bickelhaupt, F. M. (2013), Complexes of 4-substituted phenolates with HF and HCN: Energy decomposition and electronic structure analyses of hydrogen bonding. J. Comput. Chem., 34: 696–705. doi: 10.1002/jcc.23182
- Issue published online: 20 FEB 2013
- Article first published online: 23 NOV 2012
- Manuscript Accepted: 18 OCT 2012
- Manuscript Revised: 25 SEP 2012
- Manuscript Received: 10 JUL 2012
- HPC-Europa2 program
- The Warsaw University of Technology
- The Netherlands Organization for Scientific Research (NWO-CW and NWO-NCF)
- The National Research School Combination-Catalysis (NRSC-C)
- hydrogen bond;
- substituent effect;
We have computationally studied para-X-substituted phenols and phenolates (X = NO, NO2, CHO, COMe, COOH, CONH2, Cl, F, H, Me, OMe, and OH) and their hydrogen-bonded complexes with B− and HB (B = F and CN), respectively, at B3LYP/6-311++G** and BLYP-D/QZ4P levels of theory. Our purpose is to explore the structures and stabilities of these complexes. Moreover, to understand the emerging trends, we have analyzed the bonding mechanisms using the natural bond orbital scheme as well as Kohn–Sham molecular orbital (MO) theory in combination with quantitative energy decomposition analyses [energy decomposition analysis (EDA), extended transition state-natural orbitals for chemical valence (ETS-NOCV)]. These quantitative analyses allow for the construction of a simple physical model that explains all computational observations. © 2012 Wiley Periodicals, Inc.