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On the thermodynamic stability of the intermolecular association between Lewis acids and Lewis bases: a DFT study

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Abstract

The intermolecular association of twelve combinations of six different Lewis acids and Lewis bases (i.e., R 3 A–BR′3 where A = B and Al; B = N and P; R = H, F, and C6F5; R′ = H, CH3, and C(CH3)3) was theoretically described by means of DFT calculations using the dispersion-corrected ωB97x-D and B97D functionals in conjunction with the 6-311++G(2d,2p) basis set including toluene as solvent through the PCM-SMD implicit solvent scheme. All the studied Lewis pairs appeared to be stable on the basis of computed BSSE-corrected interaction energies; however, the free energies of formation computed in solution (ΔG solv) indicate that three Lewis acid–base combinations can be considered frustrated Lewis pairs (FLPs). Besides, the four features that characterize FLPs are: (1) large distances between the acid and base centers, (2) negligible changes in the geometry of the acid, (3) weak interaction energies, and (4) non-covalent dispersion energy contributing to almost the entire interaction energy. In the present work, we introduce two ad hoc indexes intended to quantify separately the electronic and steric factors, which have a direct effect in the intermolecular association of Lewis acids and Lewis bases and can be used to distinguished FLPs from classical Lewis adducts. Based on the aforementioned ad hoc indexes, the existence of a new kind of complexes that are “intermediate” between classical complexes and FLPs is proposed.

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Acknowledgments

This work has been performed by employing the resources of the USFQ’s High Performance Computing system (HPC-USFQ). The authors would like to thank USFQ’s chancellor and collaboration grants program for financial support.

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Authors and Affiliations

  1. Universidad San Francisco de Quito, Instituto de Simulación Computacional (ISC-USFQ), Diego de Robles y Vía Interoceánica, 17-1200-841, Quito, Ecuador

    Marcos Becerra, Misael Real-Enriquez, Carlos Espinosa-Gavilanes, Cesar H. Zambrano, F. Javier Torres & Luis Rincón

  2. Departamento de Ingeniería Química, Universidad San Francisco de Quito, Grupo de Química Computacional y Teórica (QCT-USFQ), Diego de Robles y Vía Interoceánica, 17-1200-841, Quito, Ecuador

    Marcos Becerra, Misael Real-Enriquez, Carlos Espinosa-Gavilanes, Cesar H. Zambrano, F. Javier Torres & Luis Rincón

  3. Departamento de Química, Facultad de Ciencias, Universidad de Los Andes, La Hechicera, Mérida, 5101, Venezuela

    Rafael Almeida & Luis Rincón

  4. ISM, UMR 5255, Université de Bordeaux, 351, Cours de la Libération, 33405, Talence, France

    F. Javier Torres

Authors
  1. Marcos Becerra
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Correspondence to Luis Rincón.

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Published as part of the special collection of articles “CHITEL 2015 - Torino - Italy.”

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Becerra, M., Real-Enriquez, M., Espinosa-Gavilanes, C. et al. On the thermodynamic stability of the intermolecular association between Lewis acids and Lewis bases: a DFT study. Theor Chem Acc 135, 77 (2016). https://doi.org/10.1007/s00214-016-1829-5

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