Structural analogues of Hoveyda–Grubbs catalysts bearing the 1-benzofuran moiety or isopropoxy-1-benzofuran derivatives as olefin metathesis catalysts

RSC Advances ◽  
2016 ◽  
Vol 6 (26) ◽  
pp. 21423-21429 ◽  
Author(s):  
B. Trzaskowski ◽  
K. Ostrowska
Keyword(s):  
Olefin Metathesis ◽  
Computational Method ◽  
Free Energies ◽  
Grubbs Catalysts ◽  
Structural Analogues ◽  
Metathesis Catalysts ◽  
Derivatives Of

We have used the DFT/M06-D3 computational method to study structures and activation free energies for a series of Hoveyda–Grubbs-like catalysts with the isopropoxybenzene part replaced by 1-benzofuran and ten derivatives of isopropoxy-1-benzofuran.

scholarly journals The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study

2018 ◽  
Vol 14 ◽  
pp. 2872-2880 ◽  
Author(s):  
Magdalena Jawiczuk ◽  
Angelika Janaszkiewicz ◽  
Bartosz Trzaskowski
Keyword(s):  
Positive Charge ◽  
Water Soluble ◽  
Free Energies ◽  
Environment Friendly ◽  
Ancillary Ligands ◽  
Grubbs Catalysts ◽  
Bond Strengths ◽  
Metathesis Catalysts ◽  
Kinetics Of ◽  
Rare Group

Cationic carbenes are a relatively new and rare group of ancillary ligands, which have shown their superior activity in a number of challenging catalytic reactions. In ruthenium-based metathesis catalysis they are often used as ammonium tags, to provide water-soluble, environment-friendly catalysts. In this work we performed computational studies on three cationic carbenes with the formal positive charge located at different distances from the carbene carbon. We show that the predicted initiation rates of Grubbs, indenylidene, and Hoveyda–Grubbs-like complexes incorporating these carbenes show little variance and are similar to initiation rates of standard Grubbs, indenylidene, and Hoveyda–Grubbs catalysts. In all investigated cases the partial charge of the carbene carbon atom is similar, resulting in comparable Ccarbene–Ru bond strengths and Ru–P/O dissociation Gibbs free energies.

scholarly journals The SN2 reaction and its relationship with the Walden inversion, the Finkelstein and Menshutkin reactions together with theoretical calculations for the Finkelstein reaction

2021 ◽  
Author(s):  
Ibon Alkorta ◽  
José Elguero
Keyword(s):  
Linear Models ◽  
Theoretical Calculations ◽  
Computational Method ◽  
Basis Set ◽  
Free Energies ◽  
Nitrogen And Phosphorus ◽  
Atom Pairs ◽  
Leaving Groups ◽  
First Time ◽  
Nitrogen Phosphorus

AbstractThis communication gives an overview of the relationships between four reactions that although related were not always perceived as such: SN2, Walden, Finkelstein, and Menshutkin. Binary interactions (SN2 & Walden, SN2 & Menshutkin, SN2 & Finkelstein, Walden & Menshutkin, Walden & Finkelstein, Menshutkin & Finkelstein) were reported. Carbon, silicon, nitrogen, and phosphorus as central atoms and fluorides, chlorides, bromides, and iodides as lateral atoms were considered. Theoretical calculations provide Gibbs free energies that were analyzed with linear models to obtain the halide contributions. The M06-2x DFT computational method and the 6-311++G(d,p) basis set have been used for all atoms except for iodine where the effective core potential def2-TZVP basis set was used. Concerning the central atom pairs, carbon/silicon vs. nitrogen/phosphorus, we reported here for the first time that the effect of valence expansion was known for Si but not for P. Concerning the lateral halogen atoms, some empirical models including the interaction between F and I as entering and leaving groups explain the Gibbs free energies.

Activated Hoveyda‐Grubbs Olefin Metathesis Catalysts Derived from a Large Scale Produced Pharmaceutical Intermediate—Sildenafil Aldehyde

2021 ◽  
Author(s):  
Louis Monsigny ◽  
Jakub Piątkowski ◽  
Damian Trzybiński ◽  
Krzysztof Wozniak ◽  
Tomasz Nienałtowski ◽  
...  
Keyword(s):  
Olefin Metathesis ◽  
Large Scale ◽  
Metathesis Catalysts

Nitrenium ions and trivalent boron ligands as analogues of N-heterocyclic carbenes in olefin metathesis: a computational study

2015 ◽  
Vol 44 (46) ◽  
pp. 20021-20026 ◽  
Author(s):  
A. Pazio ◽  
K. Woźniak ◽  
K. Grela ◽  
B. Trzaskowski
Keyword(s):  
Olefin Metathesis ◽  
Computational Study ◽  
Heterocyclic Carbenes ◽  
Mechanistic Study ◽  
Nitrenium Ions ◽  
Nitrenium Ion ◽  
Metathesis Catalysts

A DFT mechanistic study reveals that nitrenium ion-modified Hoveyda-like complexes are good candidates for latent metathesis catalysts, while boron-modified systems are candidates for very fast metathesis catalysts.

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