637-44-5Relevant academic research and scientific papers
Bulky 1,1′-bisphosphanoferrocenes and their coordination behaviour towards Cu(i)
Bruhn, Clemens,Buzsáki, Daniel,Dey, Subhayan,Kelemen, Zsolt,Pietschnig, Rudolf
, p. 6668 - 6681 (2020)
Two bulky mesityl substituted dppf-analogues Fe(C5H4PMes2)2 (Mes = 2,4,6-Me3C6H2, 1) and Fe(C5H4PMes2)(C5H4PPh2) (Mes = 2,4,6-Me3C6H2, Ph = C6H5, 3) have been prepared and their properties as donor ligands have been explored using heteronuclear NMR spectroscopy and in particular via1JP-Se coupling, cyclic voltammetry and DFT calculations. Based on the results obtained, a series of mono- and dinuclear Cu(i) complexes have been prepared with these new diphosphane ligands using Br-, I-, and BF4- as counter anions. For the very bulky ligand 1 rare and unprecedented double bridging complexation modes have been observed containing two non-planar Cu2Br2 units, while for the other dinuclear complexes planar Cu2Br2 units have been found. The Cu(i) complexes of 1 and 3 were then used as catalysts for CO2-fixation reaction with terminal alkynes, and complexes with ligand 3 were found to be more efficient than those with 1. DFT calculations performed on compounds 1, 3 and their Cu(i) complexes were able to verify the trend of these catalytic reactions.
Carboxylation of phenylacetylene by carbon dioxide on heterogeneous Ag-containing catalysts
Finashina,Kustov,Tkachenko,Krasovskiy,Formenova,Beletskaya
, p. 2652 - 2656 (2014)
A possibility of using heterogeneous catalysts with a low silver content for the direct carb-oxylation of phenylacetylene by carbon dioxide was demonstrated. A comparative study of the efficiency of the heterogeneous Ag-containing catalysts on different oxide supports (F-γ-Al2O3, γ-Al2O3, TiO2, SiO2) revealed that phenylpropiolic acid in the highest yield (62.1%) was achieved on the 0.5% Ag/F-Al2O3 catalysts.
Method for synthesizing acetylenic acid by using terminal alkyne and carbon dioxide
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Paragraph 0052-0056; 0055-0057; 0058-0060; 0061-0063; ..., (2021/07/24)
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing acetylenic acid by using terminal alkyne and carbon dioxide. The method comprises the experimental steps that alkyne, alkali and a solvent are added into a reaction tube, the alkyne serves as a raw material, the alkali and the solvent provide a strong alkaline environment, CO2 is introduced into a reaction container to form a carbon dioxide atmosphere, heating and stirring reaction are carried out, after the reaction is finished, cooling is carried out to the room temperature, extraction and liquid separation are carried out, a water layer is acidified, then separation and purification are further carried out, and the acetylenic acid compound is obtained. The method is carried out under the conditions of low temperature and normal pressure, does not need to add a metal catalyst, is single in product and convenient to separate, good in substrate applicability and safe and simple to operate, and has potential industrial application prospects and good economic benefits.
Pre-carbonized nitrogen-rich polytriazines for the controlled growth of silver nanoparticles: Catalysts for enhanced CO2chemical conversion at atmospheric pressure
Liu, Jian,Zhang, Xiaoyi,Wen, Bingyan,Li, Yipei,Wu, Jingjing,Wang, Zhipeng,Wu, Ting,Zhao, Rusong,Yang, Shenghong
, p. 3119 - 3127 (2021/05/25)
High catalytic activity and sufficient durability are two unavoidable key indices of an efficient heterogeneous catalyst for the direct carboxylation of terminal alkynes with CO2 conversion. Nitrogen-rich covalent triazine frameworks (CTFs) are promising substrates, while random distribution of some residual -NH2 groups brings challenges to the controlled growth of catalytic species. Here, we adopt a pre-carbonization protocol, annealing below the carbonization temperature, to eliminate the random -NH2 groups in CTFs and meanwhile to promote polycondensation degree under the premise of maintaining the pore structure. Benefiting from the improved condensation and orderly N atoms, p-CTF-250, for which CTFs are annealed at 250 °C, exhibits improved CO2 adsorption capacity and the ability to control the growth of Ag NPs. Mono-dispersed Ag NPs are generated controllably and entrapped to form Ag@p-CTF-250 catalysts. These Ag@p-CTF-250 catalysts were employed in the direct carboxylation of various terminal alkynes with CO2 under mild conditions (50 °C, 1 atm) and showed excellent catalytic activity. In addition, these catalysts have robust recyclability and can be used for at least 5 catalytic runs while retaining yield above 90%. CO2 conversion proceeds well under the synergistic effect between the high CO2 capture capability and the uniform tiny Ag NPs in Ag@p-CTF-250 "nanoreactors". The results represent an efficient strategy for controlling the growth of metallic nanoparticles in porous organic polymer substrates containing disordered heteroatoms.
Copper(I)-modified covalent organic framework for CO2 insertion to terminal alkynes
Bu, Ran,Zhang, Lin,Gao, Lu-Lu,Sun, Weng-Jie,Yang, Shuai-Liang,Gao, En-Qing
, (2020/12/21)
The carboxylation of terminal alkynes with CO2 is an attractive route for CO2 fixation and conversion, and various homogeneous Cu(I) catalysts have been explored for the reaction. However, it is still a challenge to develop efficient heterogeneous catalysts for the conversion under mild conditions. Considering that covalent organic frameworks (COFs) are emerging as versatile platforms for the design of functional materials, we developed a TpBpy-supported Cu(I) catalyst, where TpBpy is a stable imine-type porous COF furnished with rich N,N- and N,O-chelating sites for Cu(I) immobilization. The hybrid material can efficiently catalyze the conversion of CO2 and terminal alkynes to propiolic acids under relatively mild conditions (1 atm CO2, 60 ℃). The catalytic activity arises from the synergy between the organic framework of TpBpy and the Cu(I) sites. Not merely serving as a porous support to afford isolated and accessible Cu(I) sites, the organic framework itself has its own catalytic activity through the polar and basic N and O functional sites, which could activate the C–H bond and facilitate CO2 absorption. In addition, the framework also serves as a giant ligand to shift the reversible Cu(I)-catalyzed process in favor of carboxylation. The catalyst shows somewhat reduced activity after reused for three cycles owing to the oxidation of Cu(I) to Cu(II), but it can be easily regenerated by treating with KI.
Organocatalytic Strategy for the Fixation of CO2via Carboxylation of Terminal Alkynes
Shi, Jun-Bin,Bu, Qingqing,Liu, Bin-Yuan,Dai, Bin,Liu, Ning
supporting information, p. 1850 - 1860 (2021/01/14)
An organocatalytic strategy for the direct carboxylation of terminal alkynes with CO2 has been developed. The combined use of a bifunctional organocatalyst and Cs2CO3 resulted in a robust catalytic system for the preparation of a range of propiolic acid derivatives in high yields with broad substrate scope using CO2 at atmospheric pressure under mild temperatures (60 °C). This work has demonstrated that this organocatalytic method offers a competitive alternative to metal catalysis for the carboxylation of terminal alkynes and CO2. In addition, this protocol was suitable for the three-component carboxylation of terminal alkynes, alkyl halides, and CO2.
N-Heterocyclic carbene-nitrogen molybdenum catalysts for utilization of CO2
Chen, Fei,Tao, Sheng,Liu, Ning,Dai, Bin
, (2021/01/19)
Three new N-heterocyclic carbene-nitrogen molybdenum complex was synthesized, and its catalytic activity was evaluated in the cycloaddition of epoxides with CO2. The molybdenum complex combined with tetrabutyl ammonium iodide (TBAI) resulted in a catalytic system for efficient conversion of a wide range of terminal and internal epoxides under 80 °C and 5–7 bar pressure for CO2. The cooperative catalysis mechanism between molybdenum complex and TBAI was elucidated, in which molybdenum complex was used as Lewis acid, and TBAI was employed as nucleophilic reagent. In addition, the NHC-Mo catalytic system was also successfully applied for the direct carboxylation of terminal alkynes with CO2.
An efficient Ag/MIL-100(Fe) catalyst for photothermal conversion of CO2 at ambient temperature
Jing, Peng,Wu, Boyuan,Han, Zongsu,Shi, Wei,Cheng, Peng
supporting information, p. 3505 - 3508 (2021/05/04)
The conversion of CO2 under mild condition is of great importance because these reactions involving CO2 can not only produce value-added chemicals from abundant and inexpensive CO2 feedstock but also close the carbon cycle. However, the chemical inertness of CO2 requires the development of high-performance catalysts. Herein, Ag nanoparticles/MIL-100(Fe) composites were synthesized by simple impregnation-reduction method and employed as catalysts for the photothermal carboxylation of terminal alkynes with CO2. MIL-100(Fe) could stabilize Ag nanoparticles and prevent them from aggregation during catalytic process. Taking the advantages of photothermal effects and catalytic activities of both Ag nanoparticles and MIL-100(Fe), various aromatic alkynes could be converted to corresponding carboxylic acid products (86%–92% yields) with 1 atm CO2 at room temperature under visible light irradiation when using Ag nanoparticles/MIL-100(Fe) as photothermal catalysts. The catalysts also showed good recyclability with almost no loss of catalytic activity for three consecutive runs. More importantly, the catalytic performance of Ag nanoparticles/MIL-100(Fe) under visible light irradiation at room temperature was comparable to that upon heating, showing that the light source could replace conventional heating method to drive the reaction. This work provided a promising strategy of utilizing solar energy for achieving efficient CO2 conversion to value-added chemicals under mild condition.
Microwave-assisted fabrication of a mixed-ligand [Cu4(μ3-OH)2]-cluster-based metal–organic framework with coordinatively unsaturated metal sites for carboxylation of terminal alkynes with carbon dioxide
Wang, Wen-Jing,Sun, Zhong-Hua,Chen, Sheng-Chun,Qian, Jun-Feng,He, Ming-Yang,Chen, Qun
, (2021/05/24)
The development of efficient and stable metal–organic framework (MOF) catalysts with coordinatively unsaturated metal sites for modern organic synthesis is greatly important. Herein, a robust [Cu4(μ3-OH)2]-cluster-based MOF (Cu-MOF) with a mixed-ligand system was successfully fabricated by a microwave-assisted method under mild conditions. The as-prepared Cu-MOF catalyst possessing unsaturated Cu (II) sites exhibited excellent catalytic activity toward the direct carboxylation of 1-ethynylbenzene with CO2, and various propiolic acid derivatives were synthesized in moderate to good yields under optimized reaction conditions. Furthermore, the catalyst remained stable and could be easily recycled for five sequential runs without incredible decrease in catalytic efficiency.
Schiff-base molecules and COFs as metal-free catalysts or silver supports for carboxylation of alkynes with CO2
Bu, Ran,Gao, En-Qing,Liu, Xiao-Yan,Mu, Peng-Fei,Zhang, Lin
supporting information, p. 7620 - 7629 (2021/10/12)
Carboxylation of terminal alkynes with CO2 to produce propiolic acids is an atom economical and high-value route for CO2 fixation and utilization, but the conversion under mild conditions needs transition metal catalysts. In this article, we demonstrated for the first time the transition-metal-free organocatalysts for the reaction. The efficient catalysts are Schiff bases derived from 1,3,5-triformylphloroglucinol (Tp), either homogeneous (discrete molecules) or heterogeneous (covalent organic frameworks, COFs). The key catalytic sites are phenoxo and imine groups, which activate CO2 through phenoxo-CO2 complexation and also activate the C(sp)-H bond through bifurcate C-H?Nimine and C-H?Ophenoxo hydrogen bonds. The 2,2′-bipyridyl sites in the COF also contribute to the catalytic performance. The COF catalyst is less active than the molecular one but has the advantages of heterogeneous catalysis. Higher performance was also demonstrated by combining silver nanoparticles (AgNPs) with the intrinsically catalytic COF. This work opens up the potential of developing transition-metal-free catalysts for the CO2 conversion reaction and demonstrates the new prospects of COFs as tailorable platforms for heterogeneous catalysis.
