Adaptive Catalytic Systems for Chemical Energy Conversion

Bordet, Alexis; Leitner, Walter

doi:10.1002/anie.202301956

“…Finally, we demonstrated that the activity of the catalyst can be reversibly toggled between two states, by subsequently adding fluoride or [NO + ](BF 4 − ). Overall, all these characteristics qualify our system to fit within the recently defined category of ‘adaptive catalytic systems’, as it is capable of being adjusted into different states of performance in a reversible, rapid and robust manner [23] …”

Section: Discussionmentioning

confidence: 93%

Tuning the Catalytic Activity of a Pincer Complex of Rhodium(I) by Supramolecular and Redox Stimuli

Martínez‐Vivas,

Gusev,

Poyatos

et al. 2023

Angewandte Chemie

0

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We report a rhodium (I) complex [Rh(CNC‐NDI)(CO)]+, in which CNC‐NDI refers to a pincer‐CNC ligand decorated with a naphthalenediimide moiety. Due to the presence of the planar CNC ligand, and the naphthalenediimide moiety, the electronic nature of the complex can be modulated by means of supramolecular and redox stimuli, respectively. The metal complex shows a strong π−π‐stacking interaction with coronene. This interaction has an impact on the electronrichness of the metal, as demonstrated by the shifting of the ν(CO) stretching band to a lower frequency. The addition of tetrabutylammonium fluoride facilitates the sequential one‐ and two‐electron reduction of the NDI moiety of the ligand, thus rendering a situation in which the ligand can increase its electrondonor strength in two levels. The nature of the interaction with the fluoride anion was studied computationally. The catalytic activity of the [Rh(CNC‐NDI)(CO)]+ complex was tested in the cycloisomerization of alkynoic acids, where it is observed that the activity of the catalyst can be modulated between four levels of activity, which correspond to i) the use of the unmodified catalyst, ii) catalyst + coronene, iii) catalyst + 2 equivalents of fluoride, and iv) catalyst + 5 equivalents of fluoride.

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“…Overall, all these characteristics qualify our system to fit within the recently defined category of 'adaptive catalytic systems', as it is capable of being adjusted into different states of performance in a reversible, rapid and robust manner. [23] ). The reaction was carried out in CD 3 CN at 80 °C, with an initial concentration of 4-pentynoic acid of 0.33 M. Product yields determined by 1 H NMR spectroscopy using 1,3,5-trimethoxybenzene as an integration standard.…”

Section: Discussionmentioning

confidence: 99%

Tuning the Catalytic Activity of a Pincer Complex of Rhodium(I) by Supramolecular and Redox Stimuli

Martínez‐Vivas,

Gusev,

Poyatos

et al. 2023

View full text Add to dashboard Cite

We report a rhodium (I) complex [Rh(CNC‐NDI)(CO)]+, in which CNC‐NDI refers to a pincer‐CNC ligand decorated with a naphthalenediimide moiety. Due to the presence of the planar CNC ligand, and the naphthalenediimide moiety, the electronic nature of the complex can be modulated by means of supramolecular and redox stimuli, respectively. The metal complex shows a strong π−π‐stacking interaction with coronene. This interaction has an impact on the electronrichness of the metal, as demonstrated by the shifting of the ν(CO) stretching band to a lower frequency. The addition of tetrabutylammonium fluoride facilitates the sequential one‐ and two‐electron reduction of the NDI moiety of the ligand, thus rendering a situation in which the ligand can increase its electrondonor strength in two levels. The nature of the interaction with the fluoride anion was studied computationally. The catalytic activity of the [Rh(CNC‐NDI)(CO)]+ complex was tested in the cycloisomerization of alkynoic acids, where it is observed that the activity of the catalyst can be modulated between four levels of activity, which correspond to i) the use of the unmodified catalyst, ii) catalyst + coronene, iii) catalyst + 2 equivalents of fluoride, and iv) catalyst + 5 equivalents of fluoride.

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“…During the past three decades, the use of catalysts with ligands that incorporate stimulus-responsive units has appeared as an efficient way of conferring a biomimetic level of control over chemical transformations . Such level of control allows the tuning of the catalyst for specific needs and therefore can be used to enable chemical transformations that are difficult to achieve by other means.…”

Section: Introductionmentioning

confidence: 99%

Gold(I) Complex with a Photoactive Ligand Behaves as a Two-in-One Dual Metallaphotoredox Cross-Coupling Catalyst

Ruiz-Zambrana,

Poyatos,

Peris

2024

ACS Catal.

3

0

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We herein describe the use of a gold complex with a naphthalene-di-imide-functionalized N-heterocyclic carbene (NDI-NHC) ligand, which was used as a photocatalyst for a variety of reactions. Due to the presence of the naphthalene moiety in the ligand, the complex can be used for the photogeneration of singlet oxygen, behaving as a photocatalyst in the endoperoxidation and peroxidation of cyclic and acyclic alkenes, and also in the selective oxidation of a simulant of sulfur mustard to its related nontoxic sulfoxide. The same complex was used as catalyst for two model oxidative C−C coupling reactions, namely, the coupling of aryldiazonium salts with alkynylsilanes and with mesitylene. These two catalytic reactions are a good indication that the (NDI-NHC)-Au(I) complex can behave as an effective dual metallophotoredox catalyst but with the particular feature that both the photosensitizer and the metal catalyst are contained in the same compound, thus constituting a very rare type of a "two-in-one" metallophotoredox catalyst. The participation of the Au(I)/Au(III) couple in the catalytic process was demonstrated by the isolation of a Au(III) complex, which was obtained via a self-photoactivated photoredox reaction.

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Adaptive Catalytic Systems for Chemical Energy Conversion

Cited by 13 publications

References 72 publications

Tuning the Catalytic Activity of a Pincer Complex of Rhodium(I) by Supramolecular and Redox Stimuli

Tuning the Catalytic Activity of a Pincer Complex of Rhodium(I) by Supramolecular and Redox Stimuli

Tuning the Catalytic Activity of a Pincer Complex of Rhodium(I) by Supramolecular and Redox Stimuli

Gold(I) Complex with a Photoactive Ligand Behaves as a Two-in-One Dual Metallaphotoredox Cross-Coupling Catalyst

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