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

Bernardo, Carlos E. P.; Bauman, Nicholas P.; Piecuch, Piotr; Silva, Pedro J.

http://hdl.handle.net/10284/7825

Use this identifier to reference this record.

Name:	Description:	Size:	Format:
Pre-review_Evaluation of density functional methods on the geometric and energetic descriptions of species involved in Cu+-promoted catalysis.pdf		1.26 MB	Adobe PDF	Download

Send Feedback

Authors

Bernardo, Carlos E. P.

Bauman, Nicholas P.

Piecuch, Piotr

Silva, Pedro J.

Abstract(s)

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.

Keywords

DFT Cu(I) complexes MP2 CCSD(T)

URI

http://hdl.handle.net/10284/7825

Citation

Bernardo, C.E.P., Bauman, N.P., Piecuch, P. et al. (2013). Evaluation of density functional methods on the geometric and energetic descriptions of species involved in Cu+-promoted catalysis. Journal of Molecular Modeling ,19 (12) 5457–5467. https://doi.org/10.1007/s00894-013-2045-z , ISSN 1610-2940.