Ruthenium Amide Complexes – Synthesis and Catalytic Activity in Olefin Metathesis and in Ring‐Opening Polymerisation

Gawin, Anna; Pump, Eva; Slugovc, Christian; Kajetanowicz, Anna; Grela, Karol

doi:10.1002/ejic.201800251

Cited by 15 publications

(6 citation statements)

References 43 publications

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“…1 Stability, tolerance in relation to various functional groups and to reaction conditions, and the high catalytic activity of these metallo-complexes toward alkene metathesis reactions 2 have overshadowed other possible ruthenium derivations comprising P→Ru, 3 S→Ru (1) 4 and N→Ru (2) coordination bonds which are part of a five-membered chelate ring. Meanwhile, there is only limited information on the synthesis, application, and catalytic activity of ruthenium derivatives (type 2) with an N→Ru coordination bond included in the five-membered ring 5 (many of which have found practical applications), 5g−m and ruthenium complexes (type 3) where an N→Ru intramolecular bond is a part of the six-membered cycle are practically unknown. 6 At the same time, as was shown in our recent publication, 7 alkene metathesis reactions, along with ease of preparation and excellent storage stability.…”

Section: ■ Introductionmentioning

confidence: 99%

Influence of the N→Ru Coordinate Bond Length on the Activity of New Types of Hoveyda–Grubbs Olefin Metathesis Catalysts Containing a Six-Membered Chelate Ring Possessing a Ruthenium–Nitrogen Bond

et al. 2020

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An efficient approach to the synthesis of new types of Hoveyda–Grubbs catalysts containing an N→Ru bond in a six-membered chelate ring is proposed. The synthesis of the organometallic compounds is based on the interaction of ready accessible 2-vinylbenzylamines and 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine ligands with dichloro(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphane)ruthenate, and it afforded the target ruthenium complexes in 70–80% yields. Areas of practical utility and potential applications of the obtained chelates were highlighted by tests of the catalysts in different olefin cross-metathesis (CM) and ring-closing-metathesis (RCM) reactions. These experiments revealed a high catalytic performance (up to 10–2 mol %) of all the synthesized structures in a broad temperature range. The structural peculiarities of the resultant ruthenium catalysts were thoroughly investigated by X-ray crystallography, which allowed making a reliable correlation between the structure of the metallo-complexes and their catalytic properties. It was proved that the bond length between ruthenium and nitrogen in the six-membered chelate ring has the greatest effect on the stability and efficiency of the catalyst. As a rule, the shorter and stronger the N→Ru bond, the higher the stability of the complex and the worse its catalytic characteristics. In turn, the coordination N→Ru bond length can be finely tuned and varied over a wide range of values by changing the steric volume of the cyclic substituents at the nitrogen atom, which will make it possible, as appropriate, to obtain in the future metal complexes with predictable stability and the required catalytic activity. Also, it was found that complexes in which the nitrogen atom is included in the morpholine or isoquinoline rings are the most efficient catalysts in this series. An attempt to establish a correlation between the N→Ru bond length and the 1H and 13C chemical shifts in the RuCH fragment has been made.

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Section: ■ Introductionmentioning

confidence: 99%

Influence of the N→Ru Coordinate Bond Length on the Activity of New Types of Hoveyda–Grubbs Olefin Metathesis Catalysts Containing a Six-Membered Chelate Ring Possessing a Ruthenium–Nitrogen Bond

et al. 2020

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“… N–Ru complexes that are closest to this study (the top row [ 8 , 37 , 38 ], the bottom row [ 28 , 29 , 36 ]). …”

Section: Figures Schemes and Tablesmentioning

confidence: 79%

“…For instance, at the beginning of the 21st century, the third-generation Grubbs catalysts (like G-III-Br , Figure 1 ) were implemented in laboratory practice. It should also be mentioned that six-membered N→Ru complexes are successfully used not only in fine synthesis for RCM and ROMP reactions [ 28 , 29 , 30 , 31 , 32 , 33 ], but they have also been recently patented for commercial use including oil refining, gasoline reforming, and as catalysts for metathesis polymerization of dicyclopentadiene (DCPD) [ 34 , 35 , 36 , 37 , 38 ].…”

Section: Introductionmentioning

confidence: 99%

Influence of Substituents in a Six-Membered Chelate Ring of HG-Type Complexes Containing an N→Ru Bond on Their Stability and Catalytic Activity

et al. 2023

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An efficient approach to the synthesis of olefin metathesis HG-type catalysts containing an N→Ru bond in a six-membered chelate ring was proposed. For the most part, these ruthenium chelates can be prepared easily and in high yields based on the interaction between 2-vinylbenzylamines and Ind II (the common precursor for Ru-complex synthesis). It was demonstrated that the increase of the steric volume of substituents attached to the nitrogen atom and in the α-position of the benzylidene fragment leads to a dramatic decrease in the stability of the target ruthenium complexes. The bulkiest iPr substituent bonded to the nitrogen atom or to the α-position does not allow the closing of the chelate cycle. N,N-Diethyl-1-(2-vinylphenyl)propan-1-amine is a limiting case; its interaction with Ind II makes it possible to isolate the corresponding ruthenium chelate in a low yield (5%). Catalytic activity of the synthesized complexes was tested in RCM reactions and compared with α-unsubstituted catalysts obtained previously. The structural peculiarities of the final ruthenium complexes were thoroughly investigated using XRD and NMR analysis, which allowed making a reliable correlation between the structure of the complexes and their catalytic properties.

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“… 24 Finally, type IV systems display chelation via the alkylidene and anionic ligands. 25 Another prominent strategy to impose latency is to substitute the carbene moiety with an electron-donating group (Fischer carbene, type V). 26 …”

Section: Strategies In the Design Of Latent Catalystsmentioning

confidence: 99%

Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications

et al. 2020

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Conspectus The most important means for tuning and improving a catalyst’s properties is the delicate exchange of the ligand shell around the central metal atom. Perhaps for no other organometallic-catalyzed reaction is this statement more valid than for ruthenium-based olefin metathesis. Indeed, even the simple exchange of an oxygen atom for a sulfur atom in a chelated ruthenium benzylidene about a decade ago resulted in the development of extremely stable, photoactive catalysts. This Account presents our perspective on the development of dormant olefin metathesis catalysts that can be activated by external stimuli and, more specifically, the use of light as an attractive inducing agent. The insight gained from a deeper understanding of the properties of cis -dichlororuthenium benzylidenes opened the doorway for the systematic development of new and efficient light-activated olefin metathesis catalysts and catalytic chromatic-orthogonal synthetic schemes. Following this, ways to disrupt the ligand-to-metal bond to accelerate the isomerization process that produced the active precatalyst were actively pursued. Thus, we summarize herein the original thermal activation experiments and how they brought about the discoveries of photoactivation in the sulfur-chelated benzylidene family of catalysts. The specific wavelengths of light that were used to dissociate the sulfur–ruthenium bond allowed us to develop noncommutative catalytic chromatic-orthogonal processes and to combine other photochemical reactions with photoinduced olefin metathesis, including using external light-absorbing molecules as “sunscreens” to achieve novel selectivities. Alteration of the ligand sphere, including modifications of the N-heterocyclic carbene (NHC) ligand and the introduction of cyclic alkyl amino carbene (CAAC) ligands, produced more efficient light-induced activity and special chemical selectivity. The use of electron-rich sulfoxides and, more prominently, phosphites as the agents that induce latency widened the spectrum of light-induced olefin metathesis reactions even further by expanding the colors of light that may now be used to activate the catalysts, which can be used in applications such as stereolithography and 3D printing of tough metathesis-derived polymers.

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Ruthenium Amide Complexes – Synthesis and Catalytic Activity in Olefin Metathesis and in Ring‐Opening Polymerisation

Cited by 15 publications

References 43 publications

Influence of the N→Ru Coordinate Bond Length on the Activity of New Types of Hoveyda–Grubbs Olefin Metathesis Catalysts Containing a Six-Membered Chelate Ring Possessing a Ruthenium–Nitrogen Bond

Influence of the N→Ru Coordinate Bond Length on the Activity of New Types of Hoveyda–Grubbs Olefin Metathesis Catalysts Containing a Six-Membered Chelate Ring Possessing a Ruthenium–Nitrogen Bond

Influence of Substituents in a Six-Membered Chelate Ring of HG-Type Complexes Containing an N→Ru Bond on Their Stability and Catalytic Activity

Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications

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