Formation of active species from ruthenium alkylidene catalysts – an insight from computational perspective
Authors:
- Paweł Śliwa,
- Mariusz P. Mitoraj,
- Filip Sagan,
- Jarosław Handzlik
Abstract
Ruthenium alkylidene complexes are commonly used as olefin metathesis catalysts. Initiation of the catalytic process requires formation of a 14-electron active ruthenium species via dissociation of a respective ligand. In the present work, this initiation step has been computationally studied for the Grubbs-type catalysts (H2IMes)(PCy3)(Cl)2Ru=CHPh, (H2IMes)(PCy3)(Cl)2Ru=CH-CH=CMe2 and (H2IMes)(3-Br-py)2(Cl)2Ru=CHPh, and the Hoveyda-Grubbs-type catalysts (H2IMes)(Cl)2Ru=CH(o-OiPrC6H4), (H2IMes)(Cl)2Ru=CH(5-NO2-2-OiPrC6H3) and (H2IMes)(Cl)2Ru=CH(2-OiPr-3-PhC6H3), using density functional theory (DFT). Additionally, the Extended-Transition-State combined with the Natural Orbitals for the Chemical Valence (ETS-NOCV) and the Interacting Quantum Atoms (IQA) energy decomposition methods were applied. The computationally determined activity order within both families of the catalysts and the activation parameters are in agreement with reported experimental data. The significance of solvent simulation and the basis set superposition error (BSSE) correction is discussed. ETS-NOCV demonstrates that the bond between the dissociating ligand and the Ru-based fragment is largely ionic followed by the charge delocalizations: σ(Ru–P) and π(Ru–P) and the secondary CH…Cl, CH…π and CH…HC interactions. In the case of transition state structures, the majority of stabilization stems from London dispersion forces exerted by the efficient CH…Cl, CH…π and CH…HC interactions. Interestingly, the height of the electronic dissociation barriers is, however, directly connected with the prevalent (unfavourable) changes in the electrostatic and orbital interaction contributions despite the favourable relief in Pauli repulsion and geometry reorganization terms during the activation process. According to the IQA results, the isopropoxy group in the Hoveyda-Grubbs-type catalysts is an efficient donor of intra-molecular interactions which are important for the activity of these catalysts.
- Record ID
- CUTa6a588edefb04dc0ab1bfc6a7ae0fa55
- Publication categories
- ;
- Author
- Journal series
- Journal of Molecular Modeling, ISSN 1610-2940, e-ISSN 0948-5023
- Issue year
- 2019
- Vol
- 25
- No
- 11
- Pages
- [1-15]
- Article number
- 331
- Other elements of collation
- rys.; tab.; Bibliografia (na s.) - 12-15; Bibliografia (liczba pozycji) - 74; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 25, Iss. 11
- Substantive notes
- Topical Collections: Zdzislaw Latajka 70th Birthday Festschrift
- Keywords in English
- density functional theory, natural orbitals for chemical valence, extended-transition-state, Grubbs catalysts, Hoveyda-Grubbs catalysts, olefin metathesis
- DOI
- DOI:10.1007/s00894-019-4202-5 Opening in a new tab
- URL
- https://link.springer.com/article/10.1007/s00894-019-4202-5 Opening in a new tab
- Language
- eng (en) English
- License
- Score (nominal)
- 40
- Additional fields
- Indeksowana w: Scopus
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUTa6a588edefb04dc0ab1bfc6a7ae0fa55/
- URN
urn:pkr-prod:CUTa6a588edefb04dc0ab1bfc6a7ae0fa55
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