Hydrogenolysis versus Methanolysis of First- and Second-Generation Grubbs Catalysts: Rates, Speciation, and Implications for Tandem Catalysis†

2010 ◽  
Vol 29 (21) ◽  
pp. 5450-5455 ◽  
Author(s):  
Nicholas J. Beach ◽  
Kenneth D. Camm ◽  
Deryn E. Fogg
Keyword(s):  
Second Generation ◽  
Tandem Catalysis ◽  
Grubbs Catalysts ◽  
First And Second Generation

scholarly journals A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

2015 ◽  
Vol 11 ◽  
pp. 1767-1780 ◽  
Author(s):  
Albert Poater ◽  
Luigi Cavallo
Keyword(s):  
Dft Calculations ◽  
Olefin Metathesis ◽  
Second Generation ◽  
Phosphine Ligands ◽  
Grubbs Catalyst ◽  
Heterocyclic Ligand ◽  
Grubbs Catalysts ◽  
Wide Range ◽  
First And Second Generation ◽  
Comprehensive Study

During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

Theoretical characterization of first and second generation Grubbs catalysts in styrene cross-metathesis reactions: insights from conceptual DFT

2016 ◽  
Vol 6 (3) ◽  
pp. 755-766 ◽  
Author(s):  
Katherine Paredes-Gil ◽  
Pablo Jaque
Keyword(s):  
Second Generation ◽  
Reorganization Energy ◽  
Conceptual Dft ◽  
Reactivity Descriptors ◽  
Cross Metathesis ◽  
Grubbs Catalysts ◽  
Metathesis Reactions ◽  
Theoretical Characterization ◽  
First And Second Generation

Reorganization energy and DFT-based reactivity descriptors revealed important issues regarding the performance of Grubbs catalysts.

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