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

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

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

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2021

Confidentiality

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

Name of the periodical

Polyhedron

ISSN

0277-5387

e-ISSN

1873-3719

Volume of the periodical

200

Issue of the periodical within the volume

May

Country of publishing house

GB - UNITED KINGDOM

Number of pages

25

Pages from-to

115096

UT code for WoS article

000640385600015

EID of the result in the Scopus database

2-s2.0-85102033020