Catalysis by [Ga4L6]12− Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Norjmaa, Gantulga; Himo, Fahmi; Maréchal, Jean‐Didier; Ujaque, Gregori

doi:10.1002/chem.202201792

Cited by 8 publications

(4 citation statements)

References 63 publications

(140 reference statements)

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“…Motivated by studies that have attributed encapsulation-mediated rate enhancements to the electrostatic environment provided by the cage, ,− we aimed to identify if encapsulation in the Ga 4 L 6 cage alters the electrostatic characteristics of TMCs. Specifically, we compared the ESP and partial charges at each TMC metal center in solvated and cage environments (see Section ).…”

Section: Resultsmentioning

confidence: 99%

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Reinhardt,

Manetsch,

et al. 2024

Inorg. Chem.

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Metal−organic cages form well-defined microenvironments that can enhance the catalytic proficiency of encapsulated transition metal complexes (TMCs). We introduce a screening protocol to efficiently identify TMCs that are promising candidates for encapsulation in the Ga 4 L 6 12− nanocage. We obtain TMCs from the Cambridge Structural Database with geometric and electronic characteristics amenable to encapsulation and mine the text of associated manuscripts to curate TMCs with documented catalytic functionality. By docking candidate TMCs inside the nanocage cavity and carrying out electronic structure calculations, we identify a subset of successfully optimized candidates (TMC-34) and observe that encapsulated guests occupy an average of 60% of the cavity volume, in line with previous observations. Notably, some guests occupy as much as 72% of the cavity as a result of linker rotation. Encapsulation has a universal effect on the electrostatic potential (ESP), systematically decreasing the ESP at the metal center of each TMC in the TMC-34 data set, while minimally altering TMC metal partial charges. Collectively these observations support geometry-based screening of potential guests and suggest that encapsulation in Ga 4 L 6 12cages could electrostatically stabilize diverse cationic or electropositive intermediates. We highlight candidate guests with associated known reactivity and solubility most amenable for encapsulation in experimental follow-up studies.

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Section: Resultsmentioning

confidence: 99%

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Reinhardt,

Manetsch,

et al. 2024

Inorg. Chem.

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“…The Nazarov cyclisation has been computationally studied independently by Bergman, Raymond, Toste, Tantillo and co-workers, 155 and Ujaque and co-workers. 156 Both groups used MD, DFT and QM/MM methods. However, while Ujaque and co-workers investigated the parent gallium tetrahedron C2, the former employed the analogous [Al 4 L 6 ] 12− cage.…”

Section: How Does Cage Catalysis Work?mentioning

confidence: 99%

Picking the lock of coordination cage catalysis

Piskorz,

Martí-Centelles,

Spicer

et al. 2023

Chem. Sci.

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“…Computational chemistry techniques have in recent years been employed successfully to study a number of reactions taking place in host‐guest systems, elucidating origins of catalysis or rate acceleration and factors governing various selectivities [8–31] …”

Section: Introductionmentioning

confidence: 99%

Modeling Amine Methylation in Methyl Ester Cavitand

Norjmaa,

Rebek,

Himo

2024

Chemistry A European J

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Methylation of amines inside an introverted resorcinarene‐based deep methyl ester cavitand is investigated by means of molecular dynamics simulations and quantum chemical calculations. Experimentally, the cavitand has been shown to bind a number of amines and accelerate the methylation reaction by more than four orders of magnitude for some of them. Eight different amines are considered in the present study, and the geometries and energies of their binding to the cavitand are first characterized and analyzed. Next, the methyl transfer reactions are investigated and the calculated barriers are found to be in generally good agreement with experimental results. In particular, the experimentally‐observed rate acceleration in the cavitand as compared to the solution reaction is well reproduced by the calculations. The origins of this rate acceleration are analyzed by computational modifications made to the structure of the cavitand, and the role of the solvent is discussed.

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Catalysis by [Ga₄L₆]¹²⁻ Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Cited by 8 publications

References 63 publications

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Picking the lock of coordination cage catalysis

Modeling Amine Methylation in Methyl Ester Cavitand

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Catalysis by [Ga4L6]12− Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Cited by 8 publications

References 63 publications

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga4L612– Nanocage

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga4L612– Nanocage

Picking the lock of coordination cage catalysis

Modeling Amine Methylation in Methyl Ester Cavitand

Contact Info

Product

Resources

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Catalysis by [Ga₄L₆]¹²⁻ Metallocage on the Nazarov Cyclization: The Basicity of Complexed Alcohol is Key

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage