Origins of the Stereoretentive Mechanism of Olefin Metathesis with Ru-Dithiolate Catalysts

Abstract

A comprehensive computational study of stereoretentive olefin metathesis with Rudithiolate catalysts has been performed. We have determined how the dithiolate ligand enforces a side-bound mechanism and how the side-bound mechanism allows for stereochemical control over the forming olefin. We have used density functional theory (DFT) and ligand steric contour maps to elucidate the origins of stereoretentive metathesis with the goal of understanding how to design a new class of E-selective metathesis catalysts.

Supported Ru olefin metathesis catalysts via a thiolate tether

“…5,6,7 These compounds display reasonable activities, and some of them are Z-selective (1 and 2) or highly stereoretentive (4). 8 Our group has already reported the anchoring of olefin metathesis Ru complexes onto silica materials through the NHC ligand. 9 Besides obtaining highly active Ru olefin metathesis catalysts, we demonstrated the beneficial interaction and stabilization of the Ru complex with the silica surface.…”

Do two oxidants (ferric-peroxo and ferryl-oxo species) act in the biosynthesis of estrogens? A DFT calculation

“…22 The M06 functional with a 6-311+G(d,p) basis set (SDD basis set for Fe) was used to calculate the solvation single-point energies because of its improved description of nonbonding interactions that provide more accurate energy information. 23,24 Unless otherwise specied, all subsequently discussed energies refer to solvation free energy (DG sol , kcal mol À1 ) values, which were estimated as DG sol ¼ DE sol (SMD) + DG correction (gas), where DE sol refers to the calculated solvation single point energy and DG correction refers to the calculated thermal correction in the gas phase to the Gibbs free energy. To reduce the overestimation of the entropy contribution of the results, a correction of À2.6 (or 2.6) kcal mol À1 for 2 : 1 (or 1 : 2) transformations was considered.…”

Influência Do Impedimento Estérico De Ligantes Ancilares Em Complexos a Base De Ru Aplicados Em Metáteses Do Álcool E Acetato Cinamílicos

“…Na Figura 3b, estão apresentados os espectros do produto da metátese do AC com G2 como catalisador (figura com numeração catalisador, gerando uma espécie inativa para metátese e ativa para isomerização de olefinas. [26][27][28][29] Seguindo-se o caminho 1, Figura 4, há a descoordenação de uma PCy 3 e formação da espécie ativa "cat.1", simultaneamente coordenada ao substrato. Há a formação do primeiro intermediário metalociclobutano, troca entre os grupos da olefina e do carbeno, formando o primeiro produto dimérico (D1) e a espécie "cat.3".…”