Electronic effects in mixed N-heterocyclic carbene/phosphite indenylidene ruthenium metathesis catalysts

Bidal, Yannick D.; Urbina‐Blanco, César A.; Poater, Albert; Cordes, David B.; Slawin, Alexandra M. Z.; Cavallo, Luigi; Cazin, Catherine S. J.

doi:10.1039/c9dt01811e

Cited by 9 publications

(2 citation statements)

References 105 publications

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“…The different performance for the pyridine-based nucleophiles could also be rationalized from an electronic point of view. Accordingly, DFT calculations show that pyridine is much less nucleophilic according to the Parr electrophilicity 107,108 than 4 (0.051 vs 0.030), with DMAP having an intermediate electrophilicity (0.034). Chemical hardness 109,110 can also justify the different catalytic behavior, with values of 0.200, 0.216, and 0.247, for 4, DMAP, and pyridine, respectively that are in a good qualitative agreement with the experimental conversions reported in Table 2.…”

Section: Heterogenization Of Compoundmentioning

confidence: 99%

Cycloaddition of CO₂ to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations

et al. 2021

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Section: Heterogenization Of Compoundmentioning

confidence: 99%

Cycloaddition of CO₂ to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations

et al. 2021

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“…The chemoselectivity is mainly governed by the steric and electronic properties of the olefins: the olefin becomes more unreactive with higher steric protection. [53,54,55] The regioselectivity derived from the product distribution for the simplest case of olefin metathesis, i.e. propene with a 2 nd generation ethylidene Ru catalyst, was investigated by a computational approach.…”

Section:  Introductionmentioning

confidence: 99%

Regio, stereo and chemoselectivity of 2nd generation Grubbs ruthenium-catalyzed olefin metathesis

et al. 2022

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The examination of cross metathesis reactions leading to the desired product has been conducted to uncover computationally the origin of the chemo-, regio-and stereoselectivity. The comparison between the relative stabilities of all involved intermediates and products, together with the transition states, links to the probability for the respective pathway. Particularly, the respective transition states for each reaction tune the regio-and stereoselectivity because they lead to define the energy barriers needed to be overcome to form the new olefin as final product. The broad range of studied reactions with the 2 nd generation Grubbs catalysts allows concluding in detail the points to pay attention and thus helps to understand the chemo-, regio-and stereoselectivity in new olefin metathesis reactions. Here, a web-server joins all these mechanistic insights which is intented to support future predictive olefin metathesis catalysis.

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Combining Both Acceptorless Dehydrogenation and Borrowing Hydrogen Mechanisms in One System as Described by DFT Calculations

Cicolella

D’Alterio

Duran

et al. 2022

Advcd Theory and Sims

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The mechanisms for the formation of N-substituted hydrazones by coupling of alcohols and hydrazine, achieved by the sequential processes of acceptorless dehydrogenation and borrowing hydrogen, has been unveiled by density functional theory (DFT) calculations. The release of water and molecular hydrogen as subproducts, combined with the Mn-PNN pincer based catalyst describe a green environment. Mechanistically, apart from describing a complex system of three coupled catalytic pathways, calculations describe the pivotal role of two intermediates, which participate in two catalytic pathways each one. Finally, predictive catalysis plays the role to push forward this reaction toward milder conditions, and thus in line with green chemistry standards.

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Electronic effects in mixed N-heterocyclic carbene/phosphite indenylidene ruthenium metathesis catalysts

Abstract: Experimental and computational studies shed light on the role played by sacrificial ligand electronic properties on catalytic activity.

Cited by 9 publications

References 105 publications

Cycloaddition of CO₂ to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations

Cycloaddition of CO₂ to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations

Regio, stereo and chemoselectivity of 2nd generation Grubbs ruthenium-catalyzed olefin metathesis

Combining Both Acceptorless Dehydrogenation and Borrowing Hydrogen Mechanisms in One System as Described by DFT Calculations

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Electronic effects in mixed N-heterocyclic carbene/phosphite indenylidene ruthenium metathesis catalysts

Abstract: Experimental and computational studies shed light on the role played by sacrificial ligand electronic properties on catalytic activity.

Cited by 9 publications

References 105 publications

Cycloaddition of CO2 to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations

Cycloaddition of CO2 to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations

Regio, stereo and chemoselectivity of 2nd generation Grubbs ruthenium-catalyzed olefin metathesis

Combining Both Acceptorless Dehydrogenation and Borrowing Hydrogen Mechanisms in One System as Described by DFT Calculations

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Cycloaddition of CO₂ to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations

Cycloaddition of CO₂ to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations