Polyhedron, volume 200, pages 115096
Recent advancement on the mechanism of olefin metathesis by Grubbs catalysts: A computational perspective
2
TOPTEC Center, Institute of Plasma Physics, The Czech Academy of Sciences, Turnov, Czech Republic
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Publication type: Journal Article
Publication date: 2021-05-01
Materials Chemistry
Inorganic Chemistry
Physical and Theoretical Chemistry
Abstract
N -heterocyclic carbene (NHC) containing Ru catalysts are highly efficient in olefin metathesis. The computational investigation has been employed to understand the mechanism. NHC increases the catalyst efficiency through easily accessible rotameric conformation. The reaction proceeds through metallacyclobutane intermediate. Using bulky substituents over NHC and other anionic ligands leads to the chemo-, stereo-, and regio-selective product formation. The presence of alcohol, amines leads to catalyst decomposition through β hydride elimination. • Mechanistic study of the olefin metathesis using N -heterocyclic carbene (NHC) containing Ru catalyst. • NHC increases efficiency and stability through trans effect and active conformation. • Associative, dissociative, and interchange pathways of initiation. • A stable metallacyclobutane intermediate is formed, which governs product formation. • NHC types govern the chemo-, stereo, regio-selectivity of the product olefine. 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.
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- We do not take into account publications without a DOI.
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- Statistics recalculated weekly.
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Patra S. G., Das N. K. Recent advancement on the mechanism of olefin metathesis by Grubbs catalysts: A computational perspective // Polyhedron. 2021. Vol. 200. p. 115096.
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Patra S. G., Das N. K. Recent advancement on the mechanism of olefin metathesis by Grubbs catalysts: A computational perspective // Polyhedron. 2021. Vol. 200. p. 115096.
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TY - JOUR
DO - 10.1016/j.poly.2021.115096
UR - https://doi.org/10.1016/j.poly.2021.115096
TI - Recent advancement on the mechanism of olefin metathesis by Grubbs catalysts: A computational perspective
T2 - Polyhedron
AU - Patra, Shanti Gopal
AU - Das, Nirmal K.
PY - 2021
DA - 2021/05/01 00:00:00
PB - Elsevier
SP - 115096
VL - 200
SN - 0277-5387
ER -
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@article{2021_Patra,
author = {Shanti Gopal Patra and Nirmal K. Das},
title = {Recent advancement on the mechanism of olefin metathesis by Grubbs catalysts: A computational perspective},
journal = {Polyhedron},
year = {2021},
volume = {200},
publisher = {Elsevier},
month = {may},
url = {https://doi.org/10.1016/j.poly.2021.115096},
pages = {115096},
doi = {10.1016/j.poly.2021.115096}
}