Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO<sub>2</sub> Fixations

Takaishi, Kazuto; Nath, Bikash Dev; Yamada, Yuya; Kosugi, Hiroyasu; Ema, Tadashi

doi:10.1002/anie.201904224

Cited by 65 publications

(37 citation statements)

References 78 publications

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“…Reduction of the organic solvent will be beneficial for saving fossil fuels, energy, resources, and cost, and development of solvent-free reactions is important from the viewpoint of green chemistry. Recent successful examples of efficient solvent-free catalysis have encouraged further research and development . However, removing the solvent is one of the most difficult things, especially when the substrate is a solid.…”

Section: Discussionmentioning

confidence: 99%

Minimization of Amounts of Catalyst and Solvent in NHC-Catalyzed Benzoin Reactions of Solid Aldehydes: Mechanistic Consideration of Solid-to-Solid Conversion and Total Synthesis of Isodarparvinol B

et al. 2020

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Attempts were made to minimize the amounts of catalyst and solvent in the NHC-catalyzed benzoin reactions of solid aldehydes. In some case, solid-to-solid conversions proceeded in the solvent-free NHC-catalyzed benzoin reactions. Even if a mixture of the substrate, N-heterocyclic carbene (NHC) precursor, and inorganic base was initially a powdery solid, the reaction did proceed at reaction temperature lower than the melting points of each compound. The solid mixture partially melted or became a slurry or suspension in the meantime. We call this solid/liquid mixture a semisolid state. The reaction giving an optically active product was faster than that giving a racemic mixture of the same product. Melting-point depression was observed for a series of mixtures of the substrate and product in different substrate/product ratios. Solvent-free solid-to-solid conversions were accelerated by the formation of a semisolid state resulting from the melting-point depression of the solid substrate accompanied by the product formation. In the case of solid substrates with high melting points, melting-point depression was useless, and the addition of a small amount of solvent was needed. The first total synthesis of isodarparvinol B was achieved via the NHC-catalyzed intramolecular benzoin reaction using a small amount of solvent as an additive.

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Section: Discussionmentioning

confidence: 99%

Minimization of Amounts of Catalyst and Solvent in NHC-Catalyzed Benzoin Reactions of Solid Aldehydes: Mechanistic Consideration of Solid-to-Solid Conversion and Total Synthesis of Isodarparvinol B

et al. 2020

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“…To date, metal catalysts, including Fe, Co, Zn, Ni, Cu, Ru, and Pd complexes, − and organocatalysts, such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), N-heterocyclic carbenes (NHCs), ionic liquids (ILs), B(C 6 F 5 ) 3 , tetrabutylammonium fluoride (TBAF), and betaine, − have been proved to be effective for the N-formylation. Despite the encouraging catalytic performance of these systems, most of these approaches still require either harsh reaction conditions or expensive hydrogen source .…”

Section: Introductionmentioning

confidence: 99%

N-Formylation of Amines with Carbon Dioxide and Hydrogen Catalyzed by Ionic Liquid-Assisted Ru Complexes

Fang

Wang

Wei

et al. 2021

ACS Sustainable Chem. Eng.

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The N-formylation reaction of various amines with CO 2 is a promising method to utilize CO 2 for the production of high value-added chemicals. Herein, an efficient Ru catalyst system consisting of Ru complex ([PPN][Ru(CO) 3 Cl 3 ]) and the ionic liquid 1-butyl-3-methylimidazolium hydrogen phosphate ([Bmim] 2 [HPO 4 ]), has been developed for the N-formylation reaction. Activity evaluation demonstrated that the catalyst system exhibited good to excellent yields of formamides under very mild conditions with the assistance of ionic liquids (ILs). Furthermore, the catalyst system could be reused at least five times with a slight loss of activity in N-formylmorpholine production. Further characterization by 1 H nuclear magnetic resonance (NMR), 13 C NMR, and density functional theory (DFT) calculations showed that the ILs ([Bmim] 2 [HPO 4 ]) could facilitate the adsorption of CO 2 by a concerted action of both cations and anions of the ILs to form phosphorus carbonate intermediate, thus effectively promoting the reaction. DFT calculations demonstrated that the formation of Ru−H was the first step, and then the CO 2 absorbed by [Bmim] 2 [HPO 4 ] inserted directly into Ru−H by cooperating with the Ru sites to form HCOO − species. After that, formate species dissociated from Ru catalysts and dehydrated to form formamides by the catalytic action of Ru complex and the basic IL.

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“…On the one hand, the coupling reaction of CO 2 and epoxide avoids the use of toxicant phosgene; on the other hand, the cyclic carbonates can be widely used in such fields as aprotic polar solvents, as precursors for polymeric materials, and as intermediates for pharmaceutical and fine chemicals. 4 Until now, a wide range of catalysts has been developed for the cycloaddition reaction, such as polyoxometalate, 5 binary organic compounds, 6,7 ionic liquids, 8−10 metal−salen complexes, 11,12 metal/covalent organic frameworks, 13−15 functionalized periodic mesoporous organosilica, 16 and nitrogen-doped porous carbon. 17 Among these catalysts, the homogeneous organocatalysts showed excellent activities to the CO 2 cycloaddition reaction; however, the process of catalyst separation from the reaction system was tedious.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Until now, a wide range of catalysts has been developed for the cycloaddition reaction, such as polyoxometalate, binary organic compounds, , ionic liquids, − metal–salen complexes, , metal/covalent organic frameworks, − functionalized periodic mesoporous organosilica, and nitrogen-doped porous carbon . Among these catalysts, the homogeneous organocatalysts showed excellent activities to the CO 2 cycloaddition reaction; however, the process of catalyst separation from the reaction system was tedious .…”

Section: Introductionmentioning

confidence: 99%

Novel Carbon Nitride/Metal Oxide Nanocomposites as Efficient and Robust Catalysts for Coupling of CO₂ and Epoxides

Ping

Liu

et al. 2021

Ind. Eng. Chem. Res.

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Several environmentally benign graphitic carbon nitride (g-C 3 N 4 )based nanocomposites with Lewis acid−base dual functionalities were developed through the pyrolysis of deep-eutectic solvents (DESs). They were used as heterogeneous catalysts for cycloaddition of CO 2 to epoxides. The catalysts' structures and different process conditions were optimized, and a comparison of the catalytic activity was made with reported heterogeneous catalysts. Moreover, the catalyst reusability and applicability to different epoxides were examined. The results showed that the 2.0Zn@g-C 3 N 4 -550 combining with tetrabutylammonium bromide (TBAB) could efficiently and selectively convert CO 2 into the desired products under the conditions of 90 °C, 1.5 MPa CO 2 for 3.0 h. In addition, no obvious deactivation was observed after the catalyst was reused for five cycles. Based on the experimental results, a possible synergistic catalytic mechanism was finally proposed.

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Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO₂ Fixations

Cited by 65 publications

References 78 publications

Minimization of Amounts of Catalyst and Solvent in NHC-Catalyzed Benzoin Reactions of Solid Aldehydes: Mechanistic Consideration of Solid-to-Solid Conversion and Total Synthesis of Isodarparvinol B

Minimization of Amounts of Catalyst and Solvent in NHC-Catalyzed Benzoin Reactions of Solid Aldehydes: Mechanistic Consideration of Solid-to-Solid Conversion and Total Synthesis of Isodarparvinol B

N-Formylation of Amines with Carbon Dioxide and Hydrogen Catalyzed by Ionic Liquid-Assisted Ru Complexes

Novel Carbon Nitride/Metal Oxide Nanocomposites as Efficient and Robust Catalysts for Coupling of CO₂ and Epoxides

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Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO2 Fixations

Cited by 65 publications

References 78 publications

Minimization of Amounts of Catalyst and Solvent in NHC-Catalyzed Benzoin Reactions of Solid Aldehydes: Mechanistic Consideration of Solid-to-Solid Conversion and Total Synthesis of Isodarparvinol B

Minimization of Amounts of Catalyst and Solvent in NHC-Catalyzed Benzoin Reactions of Solid Aldehydes: Mechanistic Consideration of Solid-to-Solid Conversion and Total Synthesis of Isodarparvinol B

N-Formylation of Amines with Carbon Dioxide and Hydrogen Catalyzed by Ionic Liquid-Assisted Ru Complexes

Novel Carbon Nitride/Metal Oxide Nanocomposites as Efficient and Robust Catalysts for Coupling of CO2 and Epoxides

Contact Info

Product

Resources

About

Unexpected Macrocyclic Multinuclear Zinc and Nickel Complexes that Function as Multitasking Catalysts for CO₂ Fixations

Novel Carbon Nitride/Metal Oxide Nanocomposites as Efficient and Robust Catalysts for Coupling of CO₂ and Epoxides