Conversion of dilute CO<sub>2</sub> to cyclic carbonates at sub-atmospheric pressures by a simple indium catalyst

Baalbaki, Hassan A.; Roshandel, Hootan; Hein, Jason E.; Mehrkhodavandi, Parisa

doi:10.1039/d0cy02028a

Cited by 34 publications

(23 citation statements)

References 78 publications

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“…In addition, a control experiment using InCl 3 and 0.5 equiv of [TBA]N 3 resulted in 63% conversion and 62% polycarbonate selectivity but also included 37% ether linkages (Table , entry 15). This shows that the PNNO ligand suppresses the polyether formation at the indium center …”

Section: Resultsmentioning

confidence: 82%

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Indium-Catalyzed CO₂/Epoxide Copolymerization: Enhancing Reactivity with a Hemilabile Phosphine Donor

et al. 2021

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Group 13 metal complexes have emerged as powerful catalysts for transforming CO2 into added-value products. However, direct comparisons of reactivity between Al, Ga, and In catalysts are rare. We report aluminum (1), gallium (2), and indium (3) complexes supported by a half-salen H[PNNO] ligand with a pendent phosphine donor and investigate their activity as catalysts for the copolymerization of CO2 and cyclohexene oxide. In solution, the P-donor is dissociated for the Al and Ga complexes while for the In complex it exhibits hemilabile behavior. The indium complex shows higher conversion and selectivity than the Al or Ga analogues. The mechanism of the reaction was studied by NMR and FTIR spectroscopy experiments as well as structural characterization of off-cycle catalytic intermediate indium trichloride complex [(PNNO)InCl3][TBA] (4). This study highlights the impact of a hemilabile phosphine group on group 13 metals and provides a detailed analysis of the initiation step in CO2/epoxide copolymerization reactions.

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Section: Resultsmentioning

confidence: 82%

“…This shows that the PNNO ligand suppresses the polyether formation at the indium center. 72 Why Is Complex 3 More Active than 1 and 2? We conducted FTIR spectroscopy experiments to study the initiation step of CO 2 and CHO copolymerization using catalysts 1−3.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Indium-Catalyzed CO₂/Epoxide Copolymerization: Enhancing Reactivity with a Hemilabile Phosphine Donor

et al. 2021

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“…In this context, many homogeneous and heterogeneous catalysts have been reported which could effectively catalyze cycloaddition reactions at ambient conditions. For example, ionic liquids (ILs), [13] organic bases, [14] metal halides, [15] metal complexes, [16] porphyrins, [17] etc. are shown to be efficient for homogeneous catalysis.…”

Section: Introductionmentioning

confidence: 99%

Ionic Liquid Functionalized Chitosan Catalyst with Optimized Hydrophilic/Hydrophobic Structural Balance for Efficient CO₂ Fixation

et al. 2022

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In this work a series of chitosan‐based catalysts with ranging hydrophobic/hydrophilic balance are successfully prepared by varying the ionic liquid and hydrocarbon chain length attached to chitosan. The chitosan modified with eight carbon units displayed efficient catalytic activity for the conversion of a wide range of epoxides to their corresponding cyclic carbonates under 1 atmosphere pressure of carbon dioxide without cocatalyst and solvent. The optimized catalyst was able to convert even diepoxides and sterically bulky epoxides like t‐butyl glycidyl ether to their corresponding cyclic carbonates. This study provides an insight into catalyst designing based on possible molecular interaction between reactants and active sites of the catalyst.

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“…From the point of view of practical application, especially on an industrial scale, it is highly desirable that the newly synthesized organometallic complexes of transition metal ions are characterized by high stability under elevated temperature conditions and that they can be purified and stored without a protective gas atmosphere. In some applications it is also important thatdepending on the reaction conditions, these catalysts show a delayed initiation and, after initiation, promote the reaction quickly enough [25][26][27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

Dipicolinate Complexes of Oxovanadium(IV) and Dioxovanadium(V) with 2-Phenylpyridine and 4,4′-Dimethoxy-2,2′-bipyridyl as New Precatalysts for Olefin Oligomerization

et al. 2022

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Polyolefins are used in everyday life, including in the production of many types of plastic. In addition, polyolefins account for over 50% of the polymers produced in the world. After conducting the oligomerization reactions of 2-propen-1-ol, 2-chloro-2-propen-1-ol, and norborene, polyolefins are obtained. In this report, two complexes of oxovanadium(IV) and dioxovanadium(V) with dipicolinate, 2-phenylyridine, and 4,4′-dimethoxy-2,2′-bipyridyl as precatalysts for 2-propen-1-ol, 2-chloro-2-propen-1-ol, and norborene oligomerizations are prepared. We present for the first time the new dipicolinate complex compound of oxovanadium(IV) with 4,4′-dimetoxy-2,2′-bipyridyl. Both complexes were tested for catalytic activity in the oligomerization reactions of 2-propen-1-ol, 2-chloro-2-propen-1-ol, and norbornene. Both synthesized complexes showed high catalytic activity in these oligomerization reactions, except for the oligomerization of norbornene.

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Conversion of dilute CO₂ to cyclic carbonates at sub-atmospheric pressures by a simple indium catalyst

Abstract: A simple indium halide with an ammonium salt catalyst can catalyze effectively the cycloaddition of epoxide and dilute CO2. A detailed mechanistic investigation is conducted using kinetics, isotope labeling, and in situ NMR and IR experiments.

Cited by 34 publications

References 78 publications

Indium-Catalyzed CO₂/Epoxide Copolymerization: Enhancing Reactivity with a Hemilabile Phosphine Donor

Indium-Catalyzed CO₂/Epoxide Copolymerization: Enhancing Reactivity with a Hemilabile Phosphine Donor

Ionic Liquid Functionalized Chitosan Catalyst with Optimized Hydrophilic/Hydrophobic Structural Balance for Efficient CO₂ Fixation

Dipicolinate Complexes of Oxovanadium(IV) and Dioxovanadium(V) with 2-Phenylpyridine and 4,4′-Dimethoxy-2,2′-bipyridyl as New Precatalysts for Olefin Oligomerization

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Conversion of dilute CO2 to cyclic carbonates at sub-atmospheric pressures by a simple indium catalyst

Abstract: A simple indium halide with an ammonium salt catalyst can catalyze effectively the cycloaddition of epoxide and dilute CO2. A detailed mechanistic investigation is conducted using kinetics, isotope labeling, and in situ NMR and IR experiments.

Cited by 34 publications

References 78 publications

Indium-Catalyzed CO2/Epoxide Copolymerization: Enhancing Reactivity with a Hemilabile Phosphine Donor

Indium-Catalyzed CO2/Epoxide Copolymerization: Enhancing Reactivity with a Hemilabile Phosphine Donor

Ionic Liquid Functionalized Chitosan Catalyst with Optimized Hydrophilic/Hydrophobic Structural Balance for Efficient CO2 Fixation

Dipicolinate Complexes of Oxovanadium(IV) and Dioxovanadium(V) with 2-Phenylpyridine and 4,4′-Dimethoxy-2,2′-bipyridyl as New Precatalysts for Olefin Oligomerization

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Conversion of dilute CO₂ to cyclic carbonates at sub-atmospheric pressures by a simple indium catalyst

Indium-Catalyzed CO₂/Epoxide Copolymerization: Enhancing Reactivity with a Hemilabile Phosphine Donor

Indium-Catalyzed CO₂/Epoxide Copolymerization: Enhancing Reactivity with a Hemilabile Phosphine Donor

Ionic Liquid Functionalized Chitosan Catalyst with Optimized Hydrophilic/Hydrophobic Structural Balance for Efficient CO₂ Fixation