135682-18-7Relevant articles and documents
Hollow and microporous catalysts bearing Cr(III)-F porphyrins for room temperature CO2 fixation to cyclic carbonates
Kim, Myung Hyun,Song, Taemoon,Seo, Ue Ryung,Park, Ji Eun,Cho, Kyoungil,Lee, Sang Moon,Kim, Hae Jin,Ko, Yoon-Joo,Chung, Young Keun,Son, Seung Uk
, p. 23612 - 23619 (2017)
Hollow and microporous metal free/Cr-porphyrin networks were prepared via the Sonogashira coupling of metal-free or Cr-tetra(4-ethynylphenyl) porphyrins and 1,4-diiodobenzene on the surface of silica templates followed by silica etching. Zinc was introduced into a hollow and microporous metal free porphyrin network (H-MPN) through post-synthetic modification to form a H-MZnPN. Hollow and microporous Cr(iii)-F porphyrin networks (H-MCrPNs) showed the best catalytic activities in room temperature CO2 fixation with epoxides to cyclic carbonates. In addition, the H-MCrPN could be reused at least for five runs, maintaining the original catalytic activity. The good performance of the H-MCrPN is attributed to its microporosity, the shortened diffusion pathways for substrates due to the hollow structure, and the efficient Lewis acidic activity of Cr(iii)-F moieties.
[OSSO]-Type Fe(III) Metallate as Single-Component Catalyst for the CO2 Cycloaddition to Epoxides
Della Monica, Francesco,Buonerba, Antonio,Paradiso, Veronica,Milione, Stefano,Grassi, Alfonso,Capacchione, Carmine
, p. 283 - 288 (2019)
A new [OSSO]-Fe(III) metallate complex was prepared and characterized. We demonstrated that such metallate is the real catalytic active species for the cycloaddition of CO2 to the epoxides, formed from the in situ reaction of the related [OSSO]-Fe(III) neutral complexes and tetrabutylammonium bromide. The metallate complex was used as a single component catalyst for the formation of cyclic organic carbonates from ten epoxides and CO2 at 1 bar pressure with good activity. (Figure presented.).
Poly(hydroxyurethane): Catalytic applicability for the cyclic carbonate synthesis from epoxides and CO2
Motokucho, Suguru,Morikawa, Hiroshi
, p. 10678 - 10681 (2020)
We have developed a synthetic methodology using poly(hydroxyurethane) as an organocatalyst for the chemical fixation of CO2 into epoxides, leading to the formation of five-membered cyclic carbonates with remarkably high selectivity and yields. The catalyzed reaction was applicable to various epoxides.
Iron Coordination to Hollow Microporous Metal-Free Disalphen Networks: Heterogeneous Iron Catalysts for CO2 Fixation to Cyclic Carbonates
Cho, Kyoungil,Lee, Sang Moon,Kim, Hae Jin,Ko, Yoon-Joo,Kang, Eun Joo,Son, Seung Uk
, p. 788 - 794 (2020)
This work shows that a hollow and microporous metal-free N,N′-phenylenebis(salicylideneimine) (salphen) network (H-MSN) can be engineered by Sonogashira coupling of [tetraiodo{di(Zn-salphen)}] building blocks with 1,4-diethynylbenzene in the presence of silica templates and by successive Zn and silica etching. Iron(III) ions could be incorporated into the H-MSN to form hollow and microporous Fe–disalphen networks (H-MFeSN) with enhanced microporosity and surface area. The H-MFeSN showed efficient catalytic performance and recyclability in the CO2 conversion to cyclic carbonates.
Novel hydrazine-bridged covalent triazine polymer for CO2 capture and catalytic conversion
Liu, Anhua,Zhang, Jinju,Lv, Xiaobing
, p. 1320 - 1328 (2018)
Carbon dioxide (CO2) capture and catalytic conversion has become an attractive and challenging strategy for CO2 utilization since it is an abundant, inexpensive, and renewable C1 resource and a main greenhouse gas. Herein, a novel hydrazine-bridged covalent triazine polymer (HB-CTP) was first designed and synthesized through simple polymerization of cyanuric chloride with 2,4,6-trihydrazinyl-1,3,5-triazine. The resultant HB-CTP exhibited good CO2 capture capacity (8.2 wt%, 0 °C, and 0.1 MPa) as well as satisfactory recyclability after five consecutive adsorption-desorption cycles. Such a polymer was subsequently employed as a metal-free heterogeneous catalyst for the cyclo-addition of CO2 with various epoxides under mild and solvent-free conditions, affording cyclic carbonates with good to excellent yields (67%–99%) and high functional-group tolerance. The incorporation of hydrazine linkages into HB-CTP's architecture was suggested to play the key role in activating epoxides through hydrogen bonding. Moreover, HB-CTP can be reused at least five times without significant loss of its catalytic activity.
An efficient iron catalyst for the synthesis of five- and six-membered organic carbonates under mild conditions
Whiteoak, Christopher J.,Martin, Eddy,Belmonte, Marta Martinez,Benet-Buchholz, Jordi,Kleij, Arjan W.
, p. 469 - 476 (2012)
An iron(III) amine triphenolate complex, [FeTPhOA]2, able to efficiently catalyze the cycloaddition of carbon dioxide to a range of terminal epoxides under mild conditions, is described. In addition, it has also been found that the complex is able to catalyze the conversion with more sterically congested oxiranes and oxetanes which are generally considered challenging substrates to activate. Variation of the co-catalyst, required for ring-opening of the substrates, has also been examined. The results show that terminal epoxide substrates are converted more efficiently with an iodide co-catalyst, whereas more bulky oxirane substrates give better product yields in the presence of a bromide co-catalyst. The combined results demonstrate the broad applicability of these iron(III) complexes in this type of carbon dioxide fixation chemistry. Copyright
Zinc–Azatrane Complexes as Efficient Catalysts for the Conversion of Carbon Dioxide into Cyclic Carbonates
Bousquet, Benjamin,Martinez, Alexandre,Dufaud, Véronique
, p. 843 - 848 (2018)
Three Zn complexes based on the N4-tris(2-aminoethyl)amine (tren) chelating ligand and presenting a C3-symmetrical axis were synthesized and successfully applied in the coupling of CO2 with terminal and internal epoxides. These complexes proved to be efficient catalysts if associated with tetrabutylammonium iodide, even at a low catalyst loading (0.005 mol %) or at room temperature, and allowed the production of cyclic carbonates in good to high yields. Variation of the substitution pattern on the tren ligand was shown to impact the catalyst performance greatly, and the highest turnover number (TON) (up to 11 200) was achieved with the less sterically hindered methyl-substituted ZnII–azatrane complex. These binary Zn–azatrane/NBu4I catalytic systems could be applied to a wide range of epoxide substrates, including the more challenging internal epoxides. Moreover, although soluble in the reaction medium, Zn–azatrane catalysts could be easily recovered and reused up to three times without any substantial loss in activity, proving their robustness under the reaction conditions.
Highly Active Salen-Based Aluminum Catalyst for the Coupling of Carbon Dioxide with Epoxides at Ambient Temperature
Woo, Won Hee,Hyun, Kyunglim,Kim, Yoseph,Ryu, Ji Yeon,Lee, Junseong,Kim, Min,Park, Myung Hwan,Kim, Youngjo
, p. 5372 - 5378 (2017)
Aluminum complex [(naph)salen]AlMe [(naph)salen = N,N′-(2,3-naphthalene)bis(3,5-dimethylsalicylideneiminato)] was synthesized and fully characterized by NMR spectroscopy, high-resolution mass spectrometry, elemental analysis, and single-crystal XRD. The complex exhibits square-pyramidal geometry around the aluminum center in the solid-state structure, and it has a trigonality parameter τ of 0.13. Comparison of the catalytic activity of [(naph)salen]AlMe with that of four related aluminum complexes containing tetradentate salen ligands with different bridging groups revealed that the naphthyl-bridged salen-based aluminum complex, in conjunction with nBu4NI as cocatalyst, showed higher catalytic activity than the other complexes for the coupling of CO2 with epoxides under the mild conditions of room temperature and 5 bar of CO2 in 12 h. In addition, [(naph)salen]AlMe showed favorable features, such as requiring low catalyst loading (0.5 mol-%) and broad epoxide substrate scope, including six terminal epoxides and three internal epoxides.
Benzotriazolium ionic liquid immobilized on periodic mesoporous organosilica as an effective reusable catalyst for chemical fixation of CO2into cyclic carbonates
Hu, Yu Lin,Li, Jing Rui
, (2020)
A type of dichloro(dimethoxyethane)nickel anionic benzotriazolium ionic liquid-functionalized periodic mesoporous organosilicas were synthesized and tested as effective and practical heterogeneous catalysts in the cycloaddition of CO2 with epoxides. The catalyst PMO?ILC4H10O2NiCl3(1.0) showed brilliant catalytic activity for the synthesis of cyclic carbonates with high yields and selectivities under solvent- and cocatalyst-free conditions. We also found that the catalytic activity could be significantly influenced by the hydroxyl groups sites of periodic mesoporous organosilica and the active sites (hydroxyl groups/ dichloro(dimethoxyethane)nickel anion) of the benzotriazoliumcation ionic liquid, probably due to an intensification of intramolecular synergistic effect. The catalytic process displayed ease of recovery, excellent stability and recyclability for at least five runs without significant loss of its catalytic activity.
A Strained Ion Pair Permits Carbon Dioxide Fixation at Atmospheric Pressure by C-H H-Bonding Organocatalysis
Xu, Jiaxi,Xian, Anmei,Li, Zhenjiang,Liu, Jingjing,Zhang, Zhihao,Yan, Rui,Gao, Luoyu,Liu, Bo,Zhao, Lili,Guo, Kai
, p. 3422 - 3432 (2021)
The cycloadditions of carbon dioxide into epoxides to afford cyclic carbonates by H-bond donor (HBD) and onium halide (X) cocatalysis have emerged as a key strategy for CO2 fixation. However, if the HBD is also a halide receptor, the two will quench each other, decreasing the catalytic activity. Here, we propose a strained ion pair tris(alkylamino)cyclopropenium halide (TAC·X), in which TAC repels X. TAC possesses a positively charged cyclopropenium core that makes the vicinal C-H or N-H a nonclassical HBD. The interionic strain within TAC·X makes TAC a more electrophilic HBD, allowing it to activate the oxygen of the epoxide and making X more nucleophilic and better able to attack the methylene carbon of the epoxide. NMR titration spectra and computational studies were employed to probe the mechanism of the cycloaddition of CO2 to epoxides reactions under the catalysis of TAC·X. The 1H and 13C{1H}NMR titration spectra of the catalyst with the epoxide substrate unambiguously confirmed H-bonding between TAC and the epoxide. DFT computational studies identified the transition states in the ring-opening of the epoxide (TS1) and in the ring-closure of the cyclic carbonate (TS2).
