Enhancing catalytic strategy for cyclic carbonates synthesized from CO2 and epoxides by using cobaloxime-based double complex salts as catalysts

Alhafez, Anas; Aytar, Emine; Kılıç, Ahmet

doi:10.1016/j.jcou.2022.102129

Cited by 37 publications

(3 citation statements)

References 63 publications

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“…Currently, several highly efficient and selective metal-based catalytic systems enable the reaction between CO 2 and epoxides under mild conditions. ,− Some representative examples are metalloporphyrin-based catalysts, − aminophenolate complexes, − salophen complexes, ,− bimetallic salophen complexes, , bimetallic Robson complexes, − and bimetallic macrocyclic complexes (Figure ). , These homogeneous catalysts commonly allow the solvent-free synthesis of cyclic carbonate at room temperature or low temperatures between 25 and 120 °C with CO 2 pressures in the range of 1–50 bar. , …”

Section: Introductionmentioning

confidence: 99%

Air-Stable Cobalt(III) and Chromium(III) Complexes as Single-Component Catalysts for the Activation of Carbon Dioxide and Epoxides

Fonseca-López,

Ezenarro-Salcedo,

Nachtigall

et al. 2024

Inorg. Chem.

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Cobalt(III) and chromium(III) salophen chloride complexes were synthesized and tested for the cycloaddition of carbon dioxide (CO 2 ) with epoxides to obtain cyclic carbonates. The cat1, cat2, cat4, and cat5 complexes presented high catalytic activity without cocatalysts and are solvent-free at 100 °C, 8 bar, and 9 h. At these conditions, the terminal epoxides (1a−1k) were successfully converted into the corresponding cyclic carbonates with a maximum conversion of ∼99%. Moreover, cat5 was highlighted due to its capability of opening internal epoxides such as limonene oxide (1l) with a 36% conversion to limonene carbonate (2l), and from cyclohexene oxide (1m), cyclic trans-cyclohexene carbonate (2m) and poly(cyclohexene carbonate) were obtained with 15% and 85% selectivity, respectively. A study of the coupling reaction mechanism was proposed with the aid of electrospray ionization mass spectrometry (ESI-MS) analysis, confirming the single-component behavior of the complexes through their ionization due to epoxide coordination. In addition, crystallographic analysis of cat1 single crystals grown in a saturated solution of pyridine helped to demonstrate that the substitution of chloride ion by pyridine ligands to form an octahedral coordination occurs (Py-cat1), supporting the proposed mechanism. Also, a recyclability study was performed for cat5, and a total turnover number of 952 was obtained with only minor losses in catalytic activity after five cycles.

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Section: Introductionmentioning

confidence: 99%

Air-Stable Cobalt(III) and Chromium(III) Complexes as Single-Component Catalysts for the Activation of Carbon Dioxide and Epoxides

Fonseca-López,

Ezenarro-Salcedo,

Nachtigall

et al. 2024

Inorg. Chem.

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“…Over the past two decades, various active heterogeneous catalytic systems, including metal oxides, metal carbonates, metal halides, − molecular sieves, metal-organic frameworks, − and functionalized polymers, , have been described for the CO 2 cycloaddition to epoxides. In addition, some review articles on CO 2 /epoxide coupling reactions by Kleij et al and D’Elia et al have been reported. , Furthermore, some active organo-catalysts ,− including boronate esters , and homogeneous metal complexes fabricated on various ligands like salen and supported surfaces like silica , and metal centers such as cobalt, − uninuclear and binuclear aluminum, − zinc, , chromium, , iron, , tin, silver, scandium and yttrium, and vanadium − are reported. Among the reported metal complexes, few ruthenium(II) complexes supported by well-known ligand systems like salen and porphyrin have been studied for the CO 2 /epoxide coupling reaction.…”

Section: Introductionmentioning

confidence: 99%

Formation of Value-Added Cyclic Carbonates by Coupling of Epoxides and CO₂by Ruthenium Pincer Hydrazone Complexes under Atmospheric Pressure

Ullah

Marwat

et al. 2023

Energy Fuels

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Transforming atmospheric CO2 into industrially valuable cyclic carbonates is of great importance and one of the attractive approaches for reducing CO2 concentration in the biosphere. However, the selectivity and conversion of ruthenium catalysts for cyclic carbonate formation via CO2 insertion to epoxides are low at high pressure. Here, a series of novel ruthenium complexes supported by ONN pincer-type hydrazone ligands were successfully generated, and their potential for CO2 valorization to cyclic carbonates was investigated. NMR, Fourier transform infrared (FT-IR), mass spectrometry, elemental analysis, and single-crystal diffraction analysis further confirmed the structures of these ruthenium compounds. These compounds were utilized for the CO2/coupling reaction after thorough characterization. Fortunately, these complexes outperform the reported ruthenium catalysts with a turn-over frequency of 833 h–1 and >99% selectivity at atmospheric pressure without any assisted cocatalyst. The designed catalyst showed consistent catalytic performance over five repeating cycles.

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“…The efficient conversion of CO 2 into a cyclic carbonate − is a crucial research area in the utilization of CO 2 . A series of highly effective catalysts for the synthesis of cyclic carbonates has been reported to overcome the thermodynamic stability and kinetic inertness of CO 2 , demonstrating an area dominated by metal catalysts. − Furthermore, a series of organocatalysts, − which are sustainable alternatives to metal catalysts, − has been developed. The advantage of the metal-free strategy lies in the absence of metal contaminants in products. − Thus, it is highly desirable to develop a new metal-free catalytic system to perform the cycloaddition reaction of CO 2 and epoxides.…”

Section: Introductionmentioning

confidence: 99%

Catalysis Conversion of Carbon Dioxide and Epoxides by Tetrahydroxydiboron To Prepare Cyclic Carbonates

Luo,

Chen,

Zhang

et al. 2023

J. Org. Chem.

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A binary catalytic system comprising tetrahydroxydiboron and tetrabutylammonium iodide (TBAI) was used to catalyze the cycloaddition of carbon dioxide (CO2) with epoxides. The tetrahydroxydiboron catalyst (9 mol %), in combination with the use of TBAI (13.5 mol %) as a nucleophile, is capable of catalyzing the cycloaddition of CO2 with various terminal epoxides under room temperature and a CO2 balloon. In addition, a range of internal epoxides, including sterically hindered bicyclic epoxides and vegetable oil-based epoxides, were suitable for the catalytic system, affording a series of cyclic carbonates in moderate to high yields. The tetrahydroxydiboron/TBAI cooperative catalytic mechanism was elucidated using Fourier transform infrared spectroscopy, nuclear magnetic resonance, and electrospray ionization-high-resolution mass spectrometry. Results reveal that the tetrahydroxydiboron catalyst exhibits dual effects, activating both CO2 and epoxides; initially, it underwent the insertion of CO2 to form a boron–CO2 adduct and subsequently activated the epoxides through interaction of the B–O bond.

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Enhancing catalytic strategy for cyclic carbonates synthesized from CO2 and epoxides by using cobaloxime-based double complex salts as catalysts

Cited by 37 publications

References 63 publications

Air-Stable Cobalt(III) and Chromium(III) Complexes as Single-Component Catalysts for the Activation of Carbon Dioxide and Epoxides

Air-Stable Cobalt(III) and Chromium(III) Complexes as Single-Component Catalysts for the Activation of Carbon Dioxide and Epoxides

Formation of Value-Added Cyclic Carbonates by Coupling of Epoxides and CO₂by Ruthenium Pincer Hydrazone Complexes under Atmospheric Pressure

Catalysis Conversion of Carbon Dioxide and Epoxides by Tetrahydroxydiboron To Prepare Cyclic Carbonates

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Enhancing catalytic strategy for cyclic carbonates synthesized from CO2 and epoxides by using cobaloxime-based double complex salts as catalysts

Cited by 37 publications

References 63 publications

Air-Stable Cobalt(III) and Chromium(III) Complexes as Single-Component Catalysts for the Activation of Carbon Dioxide and Epoxides

Air-Stable Cobalt(III) and Chromium(III) Complexes as Single-Component Catalysts for the Activation of Carbon Dioxide and Epoxides

Formation of Value-Added Cyclic Carbonates by Coupling of Epoxides and CO2by Ruthenium Pincer Hydrazone Complexes under Atmospheric Pressure

Catalysis Conversion of Carbon Dioxide and Epoxides by Tetrahydroxydiboron To Prepare Cyclic Carbonates

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Formation of Value-Added Cyclic Carbonates by Coupling of Epoxides and CO₂by Ruthenium Pincer Hydrazone Complexes under Atmospheric Pressure