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A DFT study of hydrogen and methane activation by B(C6F5)3/P(t-Bu)3 and Al(C6F5)3/P(t-Bu)3 frustrated Lewis pairs

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Abstract

This contribution presents a computational study aimed at understanding factors affecting barriers associated with the activation of the H–H bond in molecular hydrogen and the H–CH3 bond in methane mediated by intermolecular Frustrated Lewis Pairs (FLPs). The classical phosphine P(t-Bu)3 Lewis base in conjunction with two Lewis acids, B(C6F5)3 and Al(C6F5)3, were used as representative models of intermolecular FLPs. DFT calculations were performed using the dispersion corrected ωB97x-D functional, including toluene as a solvent through the PCM-SMD implicit solvent scheme. The results show that, in all cases, the activation barrier is larger for methane than for hydrogen. We conclude that the observed increase in the barrier for methane activation is due primarily to a larger distortion in methane compared to hydrogen to reach the transition state. Second, a large distortion of the Lewis acid to attain a better interaction with the σ-bond in methane was observed. Finally, we found that, for both hydrogen and methane activation, a considerable reduction in the free energy activation barrier is observed when the Lewis acid Al(C6F5)3 is used. From the results extracted in this study, we propose the use of alanes acids as good candidates for methane activation.

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Acknowledgments

This work was performed using the resources of the Universidad San Francisco de Quito’s High Performance Computing system (HPC-USFQ). N.V.-E. thanks Comisión Nacional de Investigación Científica y Tecnológica (CONICYT) for a graduate fellowship. L.R. and J.M. would like to thank USFQ’s chancellor and collaboration grants program for financial support.

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Authors and Affiliations

  1. Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Correo 22, Santiago, Chile

    Nery Villegas-Escobar & Alejandro Toro-Labbé

  2. Freiburg Institut for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 19, 79104, Freiburg, Germany

    Alejandro Toro-Labbé

  3. Universidad San Francisco de Quito, Grupo de Química Computacional y Teórica (QCT-USFQ) and Instituto de Simulación Computacional (ISC-USFQ), Colegio Politecnico de Ciencias e Ingeniería, Diego de Robles y Vía Interoceánica, 17-1200-841, Quito, Ecuador

    Marcos Becerra, Misael Real-Enriquez, Jose R. Mora & Luis Rincon

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  1. Nery Villegas-Escobar
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  2. Alejandro Toro-Labbé
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  3. Marcos Becerra
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  4. Misael Real-Enriquez
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  5. Jose R. Mora
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  6. Luis Rincon
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Corresponding author

Correspondence to Luis Rincon.

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This paper belongs to Topical Collection QUITEL 2016

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Villegas-Escobar, N., Toro-Labbé, A., Becerra, M. et al. A DFT study of hydrogen and methane activation by B(C6F5)3/P(t-Bu)3 and Al(C6F5)3/P(t-Bu)3 frustrated Lewis pairs. J Mol Model 23, 234 (2017). https://doi.org/10.1007/s00894-017-3404-y

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