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Further understanding of the Ru-centered [2+2] cycloreversion/cycloaddition involved into the interconversion of ruthenacyclobutane using the Grubbs catalysts from a reaction force analysis

  • Katherine Paredes-GilEmail author
  • Fernando Mendizábal
  • Pablo Jaque
Original Paper
  • 30 Downloads
Part of the following topical collections:
  1. QUITEL 2018 (44th Congress of Theoretical Chemists of Latin Expression)

Abstract

The chemical reactivity of the first- and second-generation Grubbs catalysts has always been a significant issue in olefin metathesis. In the present work, we study the [2+2] cycloreversion/cycloaddition and the alkylidene rotation involved into the interconversion of the ruthenacyclobutane intermediate, through the reaction force and reaction force constant analysis. It has been found that the structural contribution controls the barrier energy in the interconversion of ruthenacyclobutane via [2+2] cycloreversion/cycloaddition, which is slightly lower in the second generation of Grubbs catalysts while its electronic contribution is slightly higher, which unveils a major rigidity and donor/acceptor properties of the NHC. This finding explains a greater structural contribution in the rate constant. Moreover, on the basis of the reaction force constant, the process can be classified as “two-stage”-concerted reactions, noting a more asynchronous process when the first generation is used as a catalyst.

Finally, a similar analysis into the alkylidene rotation was performed. It was determined that [2+2] cycloreversion and alkylidene rotations take place in a sequential manner, the energy barrier is again controlled by structural reorganization, and the pathway is less asynchronous.

Keywords

Ru-centered [2+2] cycloreversion/cycloaddition Reaction force constant Grubbs catalysts Density functional calculations 

Notes

Acknowledgments

K.P-G., F.M, and P.J thank CONICYT through the FONDECYT projects 3170117, 1180158, and 1181914, respectively. Moreover, K.P-G. acknowledges “CONICYT+PAI+CONVOCATORIA NACIONAL SUBVENCIÓN A INSTALACIÓN EN LA ACADEMIA CONVOCATORIA AÑO 2018 + PAI77180024.”

Supplementary material

894_2019_4150_MOESM1_ESM.pdf (592 kb)
ESM 1 Supplementary information including the Cartesian coordinates of all computed species: i) alkene coordination with 14e- inactive and olefin to the first-generation Grubbs catalysts; ii) key points along the reaction pathways to 1st-Ru-[2+2] cycloaddition; iii) key points along the reaction pathways to 2nd-Ru-[2+2] cycloaddition; and iv) key points along the reaction pathways to the alkylidene rotation in the second-generation Grubbs catalysts. (PDF 592 kb)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Katherine Paredes-Gil
    • 1
    Email author
  • Fernando Mendizábal
    • 2
  • Pablo Jaque
    • 3
  1. 1.Programa Institucional de Fomento a la Investigación, Desarrollo e InnovaciónUniversidad Tecnológica MetropolitanaSan JoaquínChile
  2. 2.Facultad de Ciencias, Departamento de QuímicaUniversidad de ChileSantiagoChile
  3. 3.Departamento de Química Orgánica y Fisicoquímica, Facultad de Ciencias Químicas y FarmacéuticasUniversidad de ChileSantiagoChile

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