Get access

Complexes of 4-substituted phenolates with HF and HCN: Energy decomposition and electronic structure analyses of hydrogen bonding

Authors

  • Halina Szatyłowicz,

    Corresponding author
    1. Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, Warsaw PL-00-664, Poland
    • Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, Warsaw PL-00-664, Poland
    Search for more papers by this author
  • Tadeusz M. Krygowski,

    1. Department of Chemistry, Warsaw University, Pasteura 1, Warsaw PL-02-093, Poland
    Search for more papers by this author
  • Célia Fonseca Guerra,

    1. Department of Theoretical Chemistry & Amsterdam Center for Multiscale Modeling (ACMM), VU University, De Boelelaan 1083, Amsterdam NL-1081 HV, The Netherlands
    Search for more papers by this author
  • F. Matthias Bickelhaupt

    1. Department of Theoretical Chemistry & Amsterdam Center for Multiscale Modeling (ACMM), VU University, De Boelelaan 1083, Amsterdam NL-1081 HV, The Netherlands
    Search for more papers by this author

  • 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.

Abstract

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.

Ancillary