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Evaluation of density functional methods on the geometric and energetic descriptions of species involved in Cu+-promoted catalysis

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Abstract

We have evaluated the performance of 15 density functionals of diverse complexity on the geometry optimization and energetic evaluation of model reaction steps present in the proposed reaction mechanisms of Cu(I)-catalyzed indole synthesis and click chemistry of iodoalkynes and azides. The relative effect of the Cu+ ligand on the relative strength of Cu+-alkyne interactions, and the strong preference for a π-bonding mode is captured by all functionals. The best energetic correlations with MP2 are obtained with PBE0, M06-L, and PBE1PW91, which also provide good quality geometries. Furthermore, PBE0 and PBE1PW91 afford the best agreement with the high-level CCSD(T) computations of the deprotonation energies of Cu+-coordinated eneamines, where MP2 strongly disagrees with CCSD(T) and the examined DFT functionals. PBE0 also emerged as the most suitable functional for the study of the energetics and geometries of Cu+ hydrides, while at the same time correctly capturing the influence of the Cu+ ligands on the metal reactivity.

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Acknowledgments

Research at REQUIMTE is supported by Fundação para a Ciência e a Tecnologia through grant no. PEst-C/EQB/LA0006/2011. This work has been financed by FEDER through Programa Operacional Factores de Competitividade – COMPETE and by Portuguese Funds through FCT – Fundação para a Ciência e a Tecnologia under project PTDC/QUI-QUI/111288/2009. This work has also been supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (Grant No. DE-FG02-01ER15228; P.P.). Useful discussions with Professor Wei Li and Mr. Jared A. Hansen are gratefully appreciated, too.

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Authors and Affiliations

  1. REQUIMTE, Faculdade de Ciências da Saúde, University Fernando Pessoa, Rua Carlos da Maia, 296, 4200-150, Porto, Portugal

    Carlos E. P. Bernardo & Pedro J. Silva

  2. Department of Chemistry, Michigan State University, East Lansing, MI, 48824, USA

    Nicholas P. Bauman & Piotr Piecuch

Authors
  1. Carlos E. P. Bernardo
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  2. Nicholas P. Bauman
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  3. Piotr Piecuch
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  4. Pedro J. Silva
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Corresponding author

Correspondence to Pedro J. Silva.

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ESM 1

Geometries and energies of every molecule optimized with each density functional and with MP2. (DOC 1184 kb)

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Bernardo, C.E.P., Bauman, N.P., Piecuch, P. et al. Evaluation of density functional methods on the geometric and energetic descriptions of species involved in Cu+-promoted catalysis. J Mol Model 19, 5457–5467 (2013). https://doi.org/10.1007/s00894-013-2045-z

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  • DOI: https://doi.org/10.1007/s00894-013-2045-z

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