Decomposition of Ruthenium Olefin Metathesis Catalyst

Ruthenium olefin metathesis catalysts are one of the most commonly used class of catalysts. There are multiple reviews on their uses in various branches of chemistry and other sciences but a detailed review of their decomposition is missing, despite a large number of recent and important advances in this field. In particular, in the last five years several new mechanism of decomposition, both olefin-driven as well as induced by external agents, have been suggested and used to explain differences in the decomposition rates and the metathesis activities of both standard, N-heterocyclic carbene-based systems and the recently developed cyclic alkyl amino carbene-containing complexes. Here we present a review which explores the last 30 years of the decomposition studied on ruthenium olefin metathesis catalyst driven by both intrinsic features of such catalysts as well as external chemicals.

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Quest for the ideal olefin metathesis catalyst

Pure and Applied Chemistry ◽

10.1351/pac200880010031 ◽

2008 ◽

Vol 80 (1) ◽

pp. 31-43 ◽

Cited By ~ 32

Author(s):

Anna Michrowska ◽

Karol Grela

Keyword(s):

Oxygen Atom ◽

Quaternary Ammonium ◽

Olefin Metathesis ◽

Amino Group ◽

Sulfonated Polystyrene ◽

Grubbs Catalyst ◽

Metathesis Catalyst ◽

Metathesis Catalysts ◽

Novel Strategy ◽

The Ideal

Attempts were made to create a catalyst that approaches Gladysz's vision of an "ideal catalyst". Modifications of the Hoveyda-Grubbs catalyst were carried out with the aim to increase its activity and broaden the scope of its applicability to challenging metathesis reactions. This was done by introduction of an electron-withdrawing substituent on the isopropoxybenzylidene group in order to diminish the donor properties of the oxygen atom. The resulting stable and easily accessible nitro-substituted Hoveyda-Grubbs catalyst has found a number of successful applications in various research and industrial laboratories. Also, a new concept for noncovalent immobilization of a ruthenium olefin metathesis catalyst is presented. The 2-isopropoxybenzylidene ligand of Hoveyda-Grubbs carbene is further modified by an additional amino group, and immobilization is achieved by treatment with sulfonated polystyrene, forming the corresponding ammonium salt. In this novel strategy for the immobilization of ruthenium-based metathesis catalysts, the amino group plays a dual role, being first an active anchor for immobilization and secondly, after protonation, activating the catalysts by electron-donating to -withdrawing switch. The same concept has been used in the preparation of a quaternary ammonium catalyst for aqueous olefin metathesis.

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In tandem or alone: a remarkably selective transfer hydrogenation of alkenes catalyzed by ruthenium olefin metathesis catalysts

Organic & Biomolecular Chemistry ◽

10.1039/c4ob02480j ◽

2015 ◽

Vol 13 (9) ◽

pp. 2684-2688 ◽

Cited By ~ 20

Author(s):

Grzegorz Krzysztof Zieliński ◽

Cezary Samojłowicz ◽

Tomasz Wdowik ◽

Karol Grela

Keyword(s):

Olefin Metathesis ◽

Transfer Hydrogenation ◽

Selective Transfer ◽

Metathesis Reaction ◽

Metathesis Catalyst ◽

Selective System ◽

Metathesis Catalysts

A remarkably selective system for transfer hydrogenation of alkenes, composed of Grubbs’ ruthenium metathesis catalyst and HCOONa/HCOOH, is presented. This system can also be formed directly after a metathesis reaction to effect hydrogenation in a single-pot.

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MOF Encapsulation of Ru Olefin Metathesis Catalysts to Block Catalyst Decomposition

Catalysts ◽

10.3390/catal10060687 ◽

2020 ◽

Vol 10 (6) ◽

pp. 687

Author(s):

Gerard Pareras ◽

Davide Tiana ◽

Albert Poater

Keyword(s):

Olefin Metathesis ◽

Density Functional ◽

Metal Organic Framework ◽

Functional Theory ◽

Ammonium N ◽

Metathesis Catalyst ◽

Metal Organic ◽

Non Covalent Interactions ◽

Metathesis Catalysts

In the present work, a catalyst variation of the second-generation Hoveyda–Grubbs catalyst, particularly the ammonium-tagged Ru-alkylidene metathesis catalyst AquaMetTM, is under study, not simply to increase the efficiency in olefin metathesis but also the solubility in polar solvents. Moreover, this ionic catalyst was combined with the metal organic framework (MOF) (Cr)MIL-101-SO3−(Na·15-crown-5)+. We started from the experimental results by Grela et al., who increased the performance when the ruthenium catalyst was confined inside the cavities of the MOF, achieving non-covalent interactions between both moieties. Here, using density functional theory (DFT) calculations, the role of the ammonium N-heterocyclic carbene (NHC) tagged and the confinement effects are checked. The kinetics are used to compare reaction profiles, whereas SambVca steric maps and NCI plots are used to characterize the role of the MOF structurally and electronically.

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Vortex Fluidic Ethenolysis, Integrating a Rapid Quench of Ruthenium Olefin Metathesis Catalysts

Australian Journal of Chemistry ◽

10.1071/ch20005 ◽

2020 ◽

Vol 73 (12) ◽

pp. 1138

Author(s):

Scott J. Pye ◽

Justin M. Chalker ◽

Colin L. Raston

Keyword(s):

Thin Film ◽

Olefin Metathesis ◽

Continuous Flow ◽

Rapid Quenching ◽

Flow Process ◽

Rapid Quench ◽

Metathesis Catalyst ◽

Fluidic Device ◽

Continuous Flow Process ◽

Metathesis Catalysts

Ruthenium-catalysed ethenolysis occurs in a vortex fluidic device (VFD) – a scalable, thin-film microfluidic continuous flow process. This process takes advantage of the efficient mass transfer of gaseous reagents into the dynamic thin film of liquid. Also reported is the rapid quenching of the ruthenium-based olefin metathesis catalyst by the addition of a saturated solution of N-acetyl-l-cysteine in MeCN, as a convenient alternative to previously reported quenching methods.

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Theoretical Investigations of Heterogeneous Olefin Metathesis Catalysts

Current Organic Chemistry ◽

10.2174/13852728113179990119 ◽

2013 ◽

Vol 17 (22) ◽

pp. 2796-2813 ◽

Cited By ~ 11

Author(s):

Jaroslaw Handzlik ◽

Kamil Kurleto

Keyword(s):

Olefin Metathesis ◽

Theoretical Investigations ◽

Metathesis Catalysts

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Activated Hoveyda‐Grubbs Olefin Metathesis Catalysts Derived from a Large Scale Produced Pharmaceutical Intermediate—Sildenafil Aldehyde

Advanced Synthesis & Catalysis ◽

10.1002/adsc.202100669 ◽

2021 ◽

Author(s):

Louis Monsigny ◽

Jakub Piątkowski ◽

Damian Trzybiński ◽

Krzysztof Wozniak ◽

Tomasz Nienałtowski ◽

...

Keyword(s):

Olefin Metathesis ◽

Large Scale ◽

Metathesis Catalysts

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A Light-Activated Olefin Metathesis Catalyst Equipped with a Chromatic Orthogonal Self-Destruct Function

Angewandte Chemie ◽

10.1002/ange.201508966 ◽

2015 ◽

Vol 128 (2) ◽

pp. 774-777 ◽

Cited By ~ 10

Author(s):

Revannath L. Sutar ◽

Efrat Levin ◽

Danielle Butilkov ◽

Israel Goldberg ◽

Ofer Reany ◽

...

Keyword(s):

Olefin Metathesis ◽

Metathesis Catalyst

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Nitrenium ions and trivalent boron ligands as analogues of N-heterocyclic carbenes in olefin metathesis: a computational study

Dalton Transactions ◽

10.1039/c5dt03446a ◽

2015 ◽

Vol 44 (46) ◽

pp. 20021-20026 ◽

Cited By ~ 10

Author(s):

A. Pazio ◽

K. Woźniak ◽

K. Grela ◽

B. Trzaskowski

Keyword(s):

Olefin Metathesis ◽

Computational Study ◽

Heterocyclic Carbenes ◽

Mechanistic Study ◽

Nitrenium Ions ◽

Nitrenium Ion ◽

Metathesis Catalysts

A DFT mechanistic study reveals that nitrenium ion-modified Hoveyda-like complexes are good candidates for latent metathesis catalysts, while boron-modified systems are candidates for very fast metathesis catalysts.

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