Cyclic carbonate synthesis from CO2 and epoxides using zinc(II) complexes of arylhydrazones of β-diketones

Montoya, C.A.; Gómez, Clara F.; Paninho, Ana B.; Nunes, Ana V. M.; Mahmudov, Kamran T.; Najdanovic‐Visak, Vesna; Martins, Luísa M. D. R. S.; Silva, M. Fátima C. Guedes da; Pombeiro, Armando J. L.; Ponte, Manuel Nunes da

doi:10.1016/j.jcat.2015.12.027

Cited by 65 publications

(18 citation statements)

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“…Therefore, a realistic transition from fossil carbon usage to alternative raw materials and commodities based on recycled carbon (CO 2 ) is imperative. Since current carbon capture and storage (CCS) technologies are able to capture up to 90% of the CO 2 produced [ 2 ], rendering it available in vast quantities and with satisfactory purity, a sustainable solution would entail its conversion into useful value-added commodity chemicals [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 ]. Among the possible strategies to use captured CO 2 , its catalytic reaction with epoxides to produce cyclic carbonates is one of the most promising applications as a renewable carbon source.…”

Section: Introductionmentioning

confidence: 99%

“…The interest in cyclic carbonates is driven by their wide range of chemical and technological applications. To date, a considerable number of catalytic systems have been developed (either metal or organocatalysts) for the cycloaddition of CO 2 and epoxides [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 ]. However, further improvements are needed, in particular, in (i) controlling the selectivity (to impair polycarbonates formation); (ii) achieving suitable catalytic activities for less reactive substrates (e.g., sterically hindered and internal epoxides); (iii) searching for milder efficient reaction conditions (high temperatures and pressures are ultimately associated with additional, indirect CO 2 emissions, limiting their value from a technological standpoint); and (iv) finding active and selective catalysts able to be recycled and reused in consecutive cycles.…”

Section: Introductionmentioning

confidence: 99%

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Efficient and Reusable Iron Catalyst to Convert CO2 into Valuable Cyclic Carbonates

Ribeiro

Goodrich

2021

Molecules

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The production of cyclic carbonates from CO2 cycloaddition to epoxides, using the C-scorpionate iron(II) complex [FeCl2{k3-HC(pz)3}] (pz = 1H-pyrazol-1-yl) as a catalyst, is achieved in excellent yields (up to 98%) in a tailor-made ionic liquid (IL) medium under mild conditions (80 °C; 1–8 bar). A favorable synergistic catalytic effect was found in the [FeCl2{k3-HC(pz)3}]/IL system. Notably, in addition to exhibiting remarkable activity, the catalyst is stable during ten consecutive cycles, the first decrease (11%) on the cyclic carbonate yield being observed during the 11th cycle. The use of C-scorpionate complexes in ionic liquids to afford cyclic carbonates is presented herein for the first time.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Efficient and Reusable Iron Catalyst to Convert CO2 into Valuable Cyclic Carbonates

Ribeiro

Goodrich

2021

Molecules

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“…North group also reported a μ-oxo-bridged bimetallic salen aluminum catalyst [ 18 , 19 ]. Since then, various bimetallic catalysts have been developed, including single-framed bimetallic catalysts [ 16 , 17 , 20 , 21 , 22 ], bridged bimetallic catalysts [ 18 , 19 , 23 , 24 , 25 , 26 ], ligand-separated bimetallic catalysts [ 27 , 28 ], and covalent bond-tethered catalysts [ 29 , 30 ].…”

Section: Introductionmentioning

confidence: 99%

Self-Assembled Bimetallic Aluminum-Salen Catalyst for the Cyclic Carbonates Synthesis

et al. 2021

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Bimetallic bis-urea functionalized salen-aluminum catalysts have been developed for cyclic carbonate synthesis from epoxides and CO2. The urea moiety provides a bimetallic scaffold through hydrogen bonding, which expedites the cyclic carbonate formation reaction under mild reaction conditions. The turnover frequency (TOF) of the bis-urea salen Al catalyst is three times higher than that of a μ-oxo-bridged catalyst, and 13 times higher than that of a monomeric salen aluminum catalyst. The bimetallic reaction pathway is suggested based on urea additive studies and kinetic studies. Additionally, the X-ray crystal structure of a bis-urea salen Ni complex supports the self-assembly of the bis-urea salen metal complex through hydrogen bonding.

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“…Several transition metal complexes have already exhibited high catalytic activity in different organic oxidative transformations, such as oxidation of alkanes or alcohols, epoxidation, carboxylation, hydrocarboxylation, in C-C couplings, CO 2 reduction, etc. [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. The efficiency of metal complexes in catalysis is highly dependent on their structural configuration and electronic properties [10,11,[15][16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Cu(II) and Fe(III) Complexes Derived from N-Acetylpyrazine-2-Carbohydrazide as Efficient Catalysts Towards Neat Microwave Assisted Oxidation of Alcohols

et al. 2019

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The mononuclear Cu(II) complex [Cu((kNN O-HL)(H 2 O) 2 ] (1) was synthesized using N-acetylpyrazine-2-carbohydrazide (H 2 L) and characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray crystallography. Two Fe(III) complexes derived from the same ligand viz, mononuclear [Fe((kNN O-HL)Cl 2 ] (2) and the binuclear [Fe(kNN O-HL)Cl(µ-OMe)] 2 (3) (synthesized as reported earlier), were also used in this study. The catalytic activity of these three complexes (1-3) was examined towards the oxidation of alcohols using tert-butyl hydroperoxide (TBHP) as oxidising agent under solvent-free microwave irradiation conditions. Primary and secondary benzyl alcohols (benzyl alcohol and 1-phenylethanol), and secondary aliphatic alcohols (cyclohexanol) were used as model substrates for this study. A comparison of their catalytic efficiency was performed. Complex 1 exhibited the highest activity in the presence of TEMPO as promoter for the oxidation of 1-phenylethanol with a maximum yield of 91.3% of acetophenone. Catalysts 2019, 9, 1053 2 of 15 catalytic reactions [3-9,29-40]. Although many catalysts have been developed to overcome ecological drawbacks, namely those using cheap and abundant metals, like copper and iron, metal catalytic systems operating under sustainable conditions are still challenging. Considering all the above mentioned points herein we present the synthesis of a new mononuclear Cu(II) complex, [Cu((kNN O-HL)(H 2 O) 2 ] (1), derived from the N-acetylpyrazine-2-carbohydrazide (H 2 L) ligand. Two Fe(III) complexes, the mononuclear [Fe((kNN O-HL)Cl 2 ] (2) and the binuclear [Fe(kNN O-HL)Cl(µ-OMe)] 2 (3), have also been synthesized using the same ligand as reported earlier [41]. The three complexes (1-3) were screened as catalytic precursors to assess their catalytic performances in the oxidation of alcohols. In the present investigation, we chose primary or secondary benzyl alcohols (benzyl alcohol, 1-phenyl alcohol) and secondary aliphatic alcohols (cyclohexanol) as model substrates and tert-butyl hydroperoxide (TBHP) as oxidising agent under microwave irradiation. MW irradiation acts as an alternative technique due to its simplicity and energy saving characteristics [6], usually leading to higher product yields and selectivities. In this investigation, the best catalytic conditions were optimized by comparing several cofactors like temperature, reaction time, influence of the presence of additives, etc. Results and Discussion Synthesis and CharacterizationsThe pro-ligand N-acetylpyrazine-2-carbohydrazide (H 2 L) was used to synthesize the mononuclear Cu(II) complex [Cu(kNN O-HL)(H 2 O) 2 ] (1) (Scheme 1). The Fe(III) complexes [Fe(kNN O-HL)Cl 2 ] (2) and [Fe(kNN O-HL)Cl(µ-OMe)] 2 (3) derived from the same pro-ligand were obtained by a method from the literature [41]. As previously observed, in this case, the N-acetylpyrazine-2-carbohydrazide also acts as a mononegative tridentate N,N,O donor (HL − ) towards the metal centre [41] and shows different coordination behaviour from a relate...

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Cyclic carbonate synthesis from CO2 and epoxides using zinc(II) complexes of arylhydrazones of β-diketones

Cited by 65 publications

References 34 publications

Efficient and Reusable Iron Catalyst to Convert CO2 into Valuable Cyclic Carbonates

Efficient and Reusable Iron Catalyst to Convert CO2 into Valuable Cyclic Carbonates

Self-Assembled Bimetallic Aluminum-Salen Catalyst for the Cyclic Carbonates Synthesis

Cu(II) and Fe(III) Complexes Derived from N-Acetylpyrazine-2-Carbohydrazide as Efficient Catalysts Towards Neat Microwave Assisted Oxidation of Alcohols

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