A latent ruthenium based olefin metathesis catalyst with a sterically demanding NHC ligand

Leitgeb, Anita; Abbas, Mudassar; Fischer, Roland; Poater, Albert; Cavallo, Luigi; Slugovc, Christian

doi:10.1039/c2cy20311a

Cited by 47 publications

(18 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[14] In the last decade,m any variants of the Ru-based catalysts have been disclosed. [1,15] Despite the numerous studies in the past two decades, [8][9][10][11][12] there is still the absence of a" universal" catalystf or all olefin metathesis applications;h owever,t here are smart particular solutions. [1] Additionally,t here is no rule of thumb to predict exactly why Ru-basedc atalystsw ith certain NHCs and phosphine ligandss howc atalytic activity, whereas with other ligands( including variants of NHCs and phosphines)t hey display poor performance.…”

Section: Introductionmentioning

confidence: 99%

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

Martínez

Vummaleti

Falivene

et al. 2016

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts.

show abstract

Section: Introductionmentioning

confidence: 99%

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

Martínez

Vummaleti

Falivene

et al. 2016

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…Such precatalysts are of particular interest in technical applications of ROMP, because they allow premixing of the precatalyst with monomers and storage of the mixture over longer periods of time even at elevated temperatures without concomitant polymerization. A series of latent ruthenium‐based catalysts including the use of a chelating carbene ligand similar to that used in Hoveyda‐type complexes with strongly coordinating co‐ligands using O, N, S, P and Se donor atoms as the second binding unit have been explored and are well documented 35–48. So far, most latent, ruthenium‐based olefin‐metathesis catalysts are triggered thermally.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium–Triazene Complexes as Latent Catalysts for UV‐Induced ROMP

et al. 2013

View full text Add to dashboard Cite

Three novel ruthenium(II) complexes, RuX2(IMesH2)[N,N‐diethyl‐N′‐(2‐benzylidene)triazene] [IMesH2 = 1,3‐dimesitylimidazolin‐2‐ylidene; X = Cl– (2), CF3COO– (3), C6F5COO– (4)] are described. Single‐crystal X‐ray structure analysis of compounds 2–4 revealed that the triazene ligand exists in the trans form and that the aryl‐connected nitrogen atom of the triazene binds to the ruthenium atom to form a five‐membered chelate ring. Compounds 2–4 were applied to the UV‐induced ring‐opening metathesis polymerization (ROMP) of cis‐cyclooctene (5) and dicyclopentadiene (6). Whereas all three precatalysts show pronounced thermal latency in the presence of 5 or 6, only compound 2 displays significant photo‐ROMP activity. The photoreactivity of precatalysts 2–4, which decreases with increasing electron‐withdrawing character and with decreasing pKa of the X groups, is discussed and correlated with the X‐ray data of 2–4, with low‐temperature 1H NMR measurements as well as with cyclovoltammetric measurements.

show abstract

“…This is promising since, for Ru, this is a drawback [41] and usually turns out to be the limiting step [42,43]. The energy cost is 23.1 kcal/mol for Ru but only 6.6 kcal/mol for Co.…”

Section: Resultsmentioning

confidence: 90%

In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co

et al. 2017

Self Cite

View full text Add to dashboard Cite

Density functional theory (DFT) calculations have been used to investigate the behavior of different transition metals from Groups 8 (Fe and Ru) and 9 (Co and Rh) in an already well-known catalytic mechanism, which is based on an Ru(SIMes)(PPh 3 )Cl 2 =CH(Ph) complex. As expected, Ru has proven to perform better than their Fe, Co, and Rh counterparts. Even though the topographic steric maps analysis shows no difference in sterical hindrance for any of the metal centers, geometrically, the Fe-based species show a high rigidity with shorter and stronger bonds confirmed by Mayer Bond Orders. The systems bearing Co as a metallic center might present a reactivity that is, surprisingly, too high according to conceptual DFT, which would consequently be a drawback for the formation of the fundamental species of the reaction pathway: the metallacycle intermediate.

show abstract

A latent ruthenium based olefin metathesis catalyst with a sterically demanding NHC ligand

Cited by 47 publications

References 34 publications

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

Ruthenium–Triazene Complexes as Latent Catalysts for UV‐Induced ROMP

In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co

Contact Info

Product

Resources

About

A latent ruthenium based olefin metathesis catalyst with a sterically demanding NHC ligand

Cited by 47 publications

References 34 publications

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C60 Fullerenes

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C60 Fullerenes

Ruthenium–Triazene Complexes as Latent Catalysts for UV‐Induced ROMP

In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co

Contact Info

Product

Resources

About

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes

In Silico Olefin Metathesis with Ru‐Based Catalysts Containing N‐Heterocyclic Carbenes Bearing C₆₀ Fullerenes