Recent advancement on the mechanism of olefin metathesis by Grubbs catalysts: A computational perspective

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389021%3A_____%2F21%3A00560457" target="_blank" >RIV/61389021:_____/21:00560457 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/pii/S0277538721000784?via%3Dihub" target="_blank" >https://www.sciencedirect.com/science/article/pii/S0277538721000784?via%3Dihub</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.poly.2021.115096" target="_blank" >10.1016/j.poly.2021.115096</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Recent advancement on the mechanism of olefin metathesis by Grubbs catalysts: A computational perspective

Popis výsledku v původním jazyce

The second-generation Grubbs catalyst contains N-heterocyclic carbene (NHC) coordinated to Ru center. Various such complexes have been employed as catalysts for the olefin metathesis reaction. Based on experimental results and theoretical analysis, it has been established that a cyclic four-membered metallacyclobutane is formed as an active intermediate. The use of the right computational recipe is prescribed in the context of the Grubbs catalyst. The carbene electronic structure in the catalyst and the course of the reaction are discussed. A recent computational study examined the possibility of an oxidation state as +2 or +4 in a comparative manner. Further, the role of catalysts in the chemo, regio, and stereoselectivity are also discussed. In particular, in recent years, Z selective catalysts (cyclometalated and dithiolate-containing) were developed through an in-depth understanding of the electronic and steric principles. Besides, the substituents present on the NHC carbene also plays an important role. Furthermore, the presence of a chiral backbone leads to stereoselectivity in the product. Studies also predict a more suitable catalyst for certain types of substrates. In a recent study, the effect of aromaticity while discussing alkene vs. arene substrate has been considered. Catalyst undergoes decomposition in the presence of primary alcohol and Brønsted/Lewis base. Mechanism of such type of deterioration via β hydride elimination of the metallacyclobutane intermediate are discussed. Finally, catalyst decomposition involving chelated complexes are also emphasized. Thus, such theoretical studies may help the experimental chemist reduce their effort in choosing a suitable catalyst. In this review article, recent advancements in the olefin metathesis mechanistic studies by Grubbs catalyst are comprehensively summarized.

Název v anglickém jazyce

Recent advancement on the mechanism of olefin metathesis by Grubbs catalysts: A computational perspective

Popis výsledku anglicky

The second-generation Grubbs catalyst contains N-heterocyclic carbene (NHC) coordinated to Ru center. Various such complexes have been employed as catalysts for the olefin metathesis reaction. Based on experimental results and theoretical analysis, it has been established that a cyclic four-membered metallacyclobutane is formed as an active intermediate. The use of the right computational recipe is prescribed in the context of the Grubbs catalyst. The carbene electronic structure in the catalyst and the course of the reaction are discussed. A recent computational study examined the possibility of an oxidation state as +2 or +4 in a comparative manner. Further, the role of catalysts in the chemo, regio, and stereoselectivity are also discussed. In particular, in recent years, Z selective catalysts (cyclometalated and dithiolate-containing) were developed through an in-depth understanding of the electronic and steric principles. Besides, the substituents present on the NHC carbene also plays an important role. Furthermore, the presence of a chiral backbone leads to stereoselectivity in the product. Studies also predict a more suitable catalyst for certain types of substrates. In a recent study, the effect of aromaticity while discussing alkene vs. arene substrate has been considered. Catalyst undergoes decomposition in the presence of primary alcohol and Brønsted/Lewis base. Mechanism of such type of deterioration via β hydride elimination of the metallacyclobutane intermediate are discussed. Finally, catalyst decomposition involving chelated complexes are also emphasized. Thus, such theoretical studies may help the experimental chemist reduce their effort in choosing a suitable catalyst. In this review article, recent advancements in the olefin metathesis mechanistic studies by Grubbs catalyst are comprehensively summarized.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Polyhedron

ISSN

0277-5387

e-ISSN

1873-3719

Svazek periodika

200

Číslo periodika v rámci svazku

May

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

25

Strana od-do

115096

Kód UT WoS článku

000640385600015

EID výsledku v databázi Scopus

2-s2.0-85102033020