585-29-5Relevant academic research and scientific papers
A Covalent Triazine Framework, Functionalized with Ir/N-Heterocyclic Carbene Sites, for the Efficient Hydrogenation of CO2 to Formate
Gunasekar, Gunniya Hariyanandam,Park, Kwangho,Ganesan, Vinothkumar,Lee, Kwangyeol,Kim, Nak-Kyoon,Jung, Kwang-Deog,Yoon, Sungho
, p. 6740 - 6748 (2017)
Functionalizing the recently developed porous materials such as porous organic frameworks and coordination polymer networks with active homogeneous catalytic sites would offer new opportunities in the field of heterogeneous catalysis. In this regard, a novel covalent triazine framework functionalized with an Ir(III)-N-heterocyclic carbene complex was synthesized and characterized to have a coordination environment similar to that of its structurally related molecular Ir complex. Because of the strong σ-donating and poor π-accepting characters of the N-heterocyclic carbene (NHC) ligand, the heterogenized Ir-NHC complex efficiently catalyzes the hydrogenation of CO2 to formate with a turnover frequency of up to 16000 h-1 and a turnover number of up to 24300; these are the highest values reported to date in heterogeneous catalysis for the hydrogenation of CO2 to formate.
Do all the protic ionic liquids exist as molecular aggregates in the gas phase?
Zhu, Xiao,Wang, Yong,Li, Haoran
, p. 17445 - 17448 (2011)
According to an EI-MS study of 1,1,3,3-tetramethylguanidium-based protic ionic liquids (PILs), it has been concluded that not all PILs exist as molecular aggregates in the gas phase. The detection of both ions of m/z 115.0 and m/z 116.0 for the 1,1,3,3-tetramethylguanidinium trifluoromethylsulfonate (TMGS) protic ionic liquid indicates that both the molecular and ionic aggregates co-exist in the gas phase, which is to say that the TMGS may also evaporate via the ionic aggregates just like aprotic ionic liquids. Furthermore, investigation on triethylamine-based and 1-methylimidazole-based PILs confirmed that the gas phase structure of PILs depends on both the acidity and basicity of the corresponding acid and base. This journal is the Owner Societies.
Self-assembly of photochromic diarylethene-peptide conjugates stabilized by β-sheet formation at the liquid/graphite interface
Nishitani, Nobuhiko,Hirose, Takashi,Matsuda, Kenji
, p. 5099 - 5102 (2019)
Two-dimensional (2-D) self-assembly of diarylethene (DAE)-peptide conjugates at the octanoic acid/graphite interface was investigated by scanning tunnelling microscopy (STM). The open-ring isomer of a DAE-peptide conjugate formed a stable 2-D molecular assembly with an antiparallel β-sheet structure. Quantitative analysis of surface coverage depending on concentration revealed a stronger stabilization effect of the oligopeptide than that of the alkyl group with a similar side chain length.
Eco-friendly and techno-economic conversion of CO2 into calcium formate, a valuable resource
Lee, Chul-Jin,Yoon, Ha-Jun,Yoon, Hayoung,Yoon, Sungho,Yoon, Taeksang
, p. 1738 - 1745 (2022/03/08)
The suppression of greenhouse gas emissions is being considered more important than ever, and consequently, the development of methods to produce useful CO2 conversion products with excellent techno-economic feasibility and high CO2 reduction capability is of interest. A continuous CO2 conversion system and a heterogenized hydrogenation catalyst can be used to develop a process for the efficient and selective production of Ca(HCO2)2, which has not been considered as a CO2 conversion product so far, from waste resources, including CaO. Techno-economic analysis of the entire process showed that the production cost of Ca(HCO2)2 was reduced by around 16% compared with the conventional process, indicating a high possibility of market penetration. Furthermore, the estimation of the global warming index of the process through a life-cycle assessment showed that the global warming index could be reduced by about 20% compared with that of existing Ca(HCO2)2 production processes.
PROCESS FOR PREPARING S-CONTAINING PYRIMIDINIUM COMPOUNDS
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Paragraph 0318; 0324; 0326, (2020/08/18)
The present invention relates to a process for preparing optically active compounds of formula X and intermediates thereof, wherein the variables of compound of formula X are as defined in the claims and the description.
Hydrogenation of CO2 to Formate using a Simple, Recyclable, and Efficient Heterogeneous Catalyst
Gunasekar, Gunniya Hariyanandam,Jung, Kwang-Deog,Yoon, Sungho
, (2019/03/11)
Today, one of the most imperative targets to realize the conversions of CO2 in industry is the development of practically viable catalytic systems that demonstrate excellent activity, selectivity, and durability. Herein, a simple heterogeneous Ru(III) catalyst is prepared by immobilizing commercially available RuCl3·xH2O onto a bipyridine-Functionalized covalent triazine framework, [bpy-CTF-RuCl3], for the first time. This novel catalyst efficiently hydrogenates CO2 into formate with an unprecedented turnover frequency (38800 h-1) and selectivity. In addition, the catalyst excellently maintains its efficiency over successive runs and produces a maximum final formate concentration of a2.1 M in just 2.5 h with a conversion of 12% in regard to CO2 feed. The apparent advantages of air stability, ease of handling, simplicity, the use of a readily available metal precursor, and the outstanding catalytic performance make [bpy-CTF-RuCl3] one of the possible candidates for realizing the large-Scale production of formic acid/formate by CO2 hydrogenation.
A MOF-assisted phosphine free bifunctional iron complex for the hydrogenation of carbon dioxide, sodium bicarbonate and carbonate to formate
Coufourier, Sébastien,Gaillard, Sylvain,Clet, Guillaume,Serre, Christian,Daturi, Marco,Renaud, Jean-Luc
supporting information, p. 4977 - 4980 (2019/05/21)
The hydrogenation of carbon dioxide into formic acid (FA) with Earth-abundant metals is a vibrant research area because FA is an attractive molecule for hydrogen storage. We report a cyclopentadienyl iron tricarbonyl complex that provides up to 3000 turnover number for carbon dioxide hydrogenation when combined with a catalytic amount of the chromium dicarboxylate MOF MIL-53(Cr). To date, this is the highest turnover number reported in the presence of a phosphine-free iron complex.
Bottom-Up Construction of a CO2-Based Cycle for the Photocarbonylation of Benzene, Promoted by a Rhodium(I) Pincer Complex
Anaby, Aviel,Feller, Moran,Ben-David, Yehoshoa,Leitus, Gregory,Diskin-Posner, Yael,Shimon, Linda J. W.,Milstein, David
, p. 9941 - 9950 (2016/08/19)
The use of carbon dioxide for synthetic applications presents a major goal in modern homogeneous catalysis. Rhodium-hydride PNP pincer complex 1 is shown to add CO2 in two disparate pathways: one is the expected insertion of CO2 into the metal-hydride bond, and the other leads to reductive cleavage of CO2, involving metal-ligand cooperation. The resultant rhodium-carbonyl complex was found to be photoactive, enabling the activation of benzene and formation of a new benzoyl complex. Organometallic intermediate species were observed and characterized by NMR spectroscopy and X-ray crystallography. Based on the series of individual transformations, a sequence for the photocarbonylation of benzene using CO2 as the feedstock was constructed and demonstrated for the production of benzaldehyde from benzene.
Hydricity of an Fe-H species and catalytic CO2 hydrogenation
Fong, Henry,Peters, Jonas C.
supporting information, p. 5124 - 5135 (2015/06/16)
Despite renewed interest in carbon dioxide (CO2) reduction chemistry, examples of homogeneous iron catalysts that hydrogenate CO2 are limited compared to their noble-metal counterparts. Knowledge of the thermodynamic properties of iron hydride complexes, including M-H hydricities (GH-), could aid in the development of new iron-based catalysts. Here we present the experimentally determined hydricity of an iron hydride complex: (SiPiPr3)Fe(H2)(H), GH- = 54.3 ± 0.9 kcal/mol [SiPiPr3 = [Si(o-C6H4PiPr2)3]-]. We also explore the CO2 hydrogenation chemistry of a series of triphosphinoiron complexes, each with a distinct apical unit on the ligand chelate (Si-, C-, PhB-, N, B). The silyliron (SiPR3)Fe (R = iPr and Ph) and boratoiron (PhBPiPr3)Fe (PhBPiPr3 = [PhB(CH2PiPr2)3]-) systems, as well as the recently reported (CPiPr3)Fe (CPiPr3 = [C(o-C6H4PiPr2)3]-), are also catalysts for CO2 hydrogenation in methanol and in the presence of triethylamine, generating methylformate and triethylammonium formate at up to 200 TON using (SiPPh3)FeCl as the precatalyst. Under stoichiometric conditions, the iron hydride complexes of this series react with CO2 to give formate complexes. Finally, the proposed mechanism of the (SiPiPr3)-Fe system proceeds through a monohydride intermediate (SiPiPr3)Fe(H2)(H), in contrast to that of the known and highly active tetraphosphinoiron, (tetraphos)Fe (tetraphos = P(o-C6H4PPh2)3), CO2 hydrogenation catalyst.
