JOURNAL OF ORGANIC CHEMISTRY
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2022
·
IF 4.198
Shihai Lv,Ya-Nan Tian,Yanyan Yang,Chaoying Wen,Shiqing Li
An efficient one-pot synthesis of 1,1′-biisoquinolines by a three-component reaction of commercially available raw materials (benzils, NH4OAc, and alkynes) is disclosed. This complicated reaction involves in situ diimine formation via benzil-NH4OAc condensation, Rh(III)-catalyzed 2-fold imine-directed C–H activation, and annulation with alkynes. Both symmetric and unsymmetric 1,1′-biisoquinolines could be assembled in moderate to high yields. The reaction mechanism is supported through ESI-MS, in which Cp*ClRh+, Cp*(OAc)Rh+, Cp*(OPiv)Rh+, and two rhodacycle intermediates are successfully detected to explain the evolution of rhodium species.
研究领域:
有机化学
·
合成化学
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DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2022
·Vol. 46
·期 16
·7695-7703
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IF 3.925
Qi Wu,Changfeng Zhao,Qinzhong Wang,Jing Liu
This study proposes the efficient separation of Au(III)/Pd(II)/Pt(IV)/Rh(III) through the 2-mercaptobenzothiazole-functionalised ionic liquid ([C6mim][2MBT]) using a cloud point extraction system. Direct cloud point extraction of Au(III) (about 99.9%) was realised without involving any functionalised ionic liquids. A significant enhancement of the Pd(II) extraction performance was found by adding rationally constructed [C6mim][2MBT]. Consequently, a fairly high extraction percentage of about 99.4% was obtained. However, further advancement of the proposed cloud point extraction showed that it could not be applied for the preconcentration of Pt(IV) and Rh(III) without adding stannous chloride, which plays a critical role in the segregation and could be adjusted by changing the hydrochloric acid concentration. Under the optimised conditions, the Rh(III) extraction process shows a high yield percentage (ca. 83.0%), where the majority of Pt(IV) was enriched in the aqueous phase. In addition, the underlying possible extraction mechanism was investigated using UV-vis, FT-IR and TEM measurements, which indicated that TX-114 acted as a solvent for the extracted metals. The developed procedure reveals efficient direct Au(III)/Pd(II)/Pt(IV)/Rh(III) separation using [C6mim][2MBT] via cloud point extraction.
研究领域:
分析化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Jianwei Zhang,Ronghao Liu,Xiaoxia Liu,Jun Li,Ruihui Wu,Yanzhao Yang
Rhodium, as a rare precious metal, has always been a challenge for the chemical industry to efficiently recover rhodium by extraction due to the complex existing situation in hydrochloric acid medium. Herein, a strongly hydrophobic DABCO-based ionic liquid (IL) [C 8 DABCO][NTf 2 ] was designed and synthesized to construct a solvent-free extraction system of Rh(III) from high-concentration hydrochloric acid medium. At first, the effects of some important parameters on Rh(III) extraction were studied, such as equilibrium time, IL dosage, hydrochloric acid concentration, and initial Rh(III) concentration, the results showed that 81.54% Rh(III) can be extracted under the optimum extraction conditions. Based on the experimental run results, a quadratic model equation was established by using the response surface method (RSM), which can be used to calculate the amount that [C 8 DABCO][NTf 2 ] will be offered at various HCl concentrations during the actual extraction of Rh(III). Then, using Job's method, the Ultraviolet visible spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FT-IR), Energy-dispersive X-ray spectroscopy (EDS), and Electrostatic potential (ESP) prove that the extraction mechanism is an anion exchange mechanism. Finally, in the mixed solution of multi-metals, the extraction efficiency of [C 8 DABCO][NTf 2 ] for Rh(III) is not disturbed, and the extraction efficiency for other metals is less than 1%. And the single-stage stripping efficiency of Rh(III) was up to 88% through HCl stripping, which solved the problem of difficult stripping of Rh(III) solution and realized the recycling of IL. The study provides a reliable and efficient way for recovering Rh(III) from high-concentrations HCl solutions.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
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2013
·
IF 3.187
Sheng-Jie Chen,Yong-Yong Wang,Wei-Min Yao,Xiao-Li Zhao,Giang VO-Thanh,Ye Liu
A novel ionic complex with insensitivity to moisture and air, bis-[1-butyl-2-diphenylphosphanyl-3-methylimidazolium]tetrachloridorhodium(III) hexafluorophosphate ( 1A ), has been synthesized and fully characterized. The single-crystal X-ray diffraction analysis shows that 1A is composed of the Rh(III)-complex cation and the counter-anion of PF 6 − . The complex cation has highly symmetrical Rh III -centered octahedron geometry with four Cl atoms in the equatorial plane and two imidazolium-substituted phosphine ligands in the axial position. The catalytic performance of 1A , which could be tailored by the ligands and the solvents, was investigated toward the biphasic hydroformylation of 1-octene. It was found that the presence of the hemilabile hybrid P,N-ligand of 3 (1-(2′-piperid-1′-yl-ethyl)-2-diphenylphosphino-3-methylimidazolium hexafluorophosphate), as a kind of ligand-functionalized ionic liquids (ILs), could dramatically spur the catalytic activity of 1A . The use of the RTIL of [PEmim]BF 4 (1-(2′-piperid-1′-yl-ethyl)-3-methylimidazolium tetrafluoroborate) as the solvent not only fulfilled the efficient biphasic hydroformylation of 1-octene, but also guaranteed the successful recovery and recycling of the ionic compositions of 1A and 3 .
研究领域:
化学
·
催化反应
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING RESEARCH & DESIGN
·
2023
·
IF 3.9
Dongxue Tao,Haitao Zhou,Kaihui Cui,Linchen Xie,Kun Huang
The unique characteristics of the interface environment that distinguish bulk phases can promote or inhibit certain reactions and significantly change chemical reactivity. In this work, the separation of Rh (III) and Fe (III) on the surface of concentrated hydrochloric acid was studied by a thin-layer oil membrane (TOM) extraction based on laminar flow with 18-Crown-6-ether (18C6) as the extractant. A new phenomenon different from conventional extraction was found. The TOM extraction prefers to identify hydrated Rh (III) anions rather than H 3 O + ions at the interface due to a lower concentration of free hydrated hydrogen ions on the surface of concentrated hydrochloric acid. However, during the conventional extraction, the H 3 O + ions in the bulk phase are preferentially extracted by the 18C6, and then the hydrated rhodium (III) anions could be extracted by the protonated crown ether through the ion association mechanism. Besides, it was found that the TOM extraction could enhance extraction of hydrated rhodium (III) anions by taking advantage of the uniqueness of rhodium species on the interface, and by adjusting the thickness of the oil membrane and the flow rate of the aqueous phase . The decrease in the oil membrane thickness and the increase in the flow rate of the aqueous phase are conducive to the complexation of 18C6 with the hydrated rhodium (III) at the interface, which can better reflect the targeting and the controllability of extracting single species of hydrated rhodium (III) ions at the interface. Considering the applications of selective recovery of Rh (III) from concentrated hydrochloric acid leaching solution of waste automobile catalyst, the selective separability of Rh (III) to other coexisting metal impurity ions such as Fe (III), Cu (II), Co (III) and Ni (II), was also evaluated. This work provides a new strategy for preferential recovery and separation of rhodium in concentrated hydrochloric acid leach solutions containing other base metal ions for possible future's application.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2025
·
IF 4.7
Jian-rong Teng,Jia-yi Li,Hong-hua Han,Yan-cheng Liu,Rui-xue Liu,Hong Liang
A new 9-aldehyde pyrimidylanthrahydrazone ligand (AMPAH) and its ionic Rh(III)/Ir(III) complexes were synthesized and evaluated for their potential as anticancer agents. Structural characterization by single-crystal X-ray diffraction analysis confirmed the very similar octahedral geometry for both complexes, with coordination involving DMSO and Cl⁻ moieties. Competitive DNA-binding assay suggested the effectively intercalative binding mode, by achieving the similar quenching efficiency of 83% and 84% for AMPAH-Rh and AMPAH-Ir, respectively, at quite low [GelRed]/[DNA]/[complex] molar ratio of ca. 1/10/0.3. Gel electrophoresis further confirmed the dual targets of DNA and topoisomerase I (Topo I), with AMPAH-Ir showing superior Topo I inhibition compared to AMPAH-Rh. In vitro cytotoxicity studies highlighted the selective activity of AMPAH-Ir against cancer cell lines T-24 (IC 50 = 9.05 μM) and NCI-H460 (IC 50 = 10.98 μM), surpassing the efficacy of cisplatin. Mechanistic studies revealed significant nuclear accumulation of AMPAH-Ir, together with G1-phase cell cycle arrest (59.19% at 12 μM) and early-phase apoptosis induction ( ca. 20% at 9 μM). Collectively, these results indicate that AMPAH-Ir represents a promising dual-targeting anticancer agent with and satisfying cytotoxic selectivity.
研究领域:
无机化学
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生物无机化学
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药理学
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结构生物学
✓ 已验证
产品关联
DOI
高影响因子
Journal of the American Chemical Society
·
2019
·
IF 14.695
Fangfang Wei,Shiu-Lun Lai,Shunan Zhao,Maggie Ng,Mei-Yee Chan,Vivian Wing-Wah Yam,Keith Man-Chung Wong
A series of luminescent cyclometalated rhodium(III) complexes have been designed and prepared. The improved luminescence property is realized by the judicious choice of a strong σ-donor cyclometalating ligand with a lower-lying intraligand (IL) state that would raise the d–d excited state and introduction of a lower-lying emissive IL excited state. These complexes exhibit high thermal stability and considerable luminescence quantum yields as high as up to 0.65 in thin film, offering themselves as promising light-emitting materials in OLEDs. Respectable external quantum efficiencies of up to 12.2% and operational half-lifetimes of over 3000 h at 100 cd m–2 have been achieved. This work demonstrates a breakthrough as the first example of an efficient rhodium(III) emitter for OLED application and opens up a new avenue for diversifying the development of OLED materials with rhodium metal being utilized as phosphors.
研究领域:
材料科学
·
光学
·
化学
✓ 已验证
DOI
高影响因子
ENERGY & FUELS
·
2021
·
IF 3.605
Fangfang Wei,Zhiyuan Qian,Shiu-Lun Lai,Shunan Zhao,Mei-Yee Chan,Keith Man-Chung Wong
A series of orange–red-emitting cyclometalating rhodium(III) complexes have been synthesized, characterized, and applied as phosphorescent dopants to fabricate solution-processed and vacuum-deposited organic light-emitting devices (OLEDs). Various substituents on different positions of 2,3-diphenylquinoxaline (dpqx) cyclometalating ligands were introduced. High external quantum efficiencies of 9.40% and good operational half-lifetimes of up to 17 322 h at 100 cd m–2 were achieved. The results revealed that the fluorine atoms might improve the electroluminescence performance in terms of device lifetime, demonstrating the potential suitable phosphorescent materials for OLED application.
研究领域:
材料科学
·
光学工程
✓ 已验证
产品关联
DOI
高影响因子
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
·
2012
·Vol. 638
·期 6
·1039-1041
·
IF 1.249
Liyong Du,Songlin Zhang,Yuqiang Ding
A carbonate-bridged rhodium(III) dimeric complex of formula μ-CO 3 -[(ppy) 2 Rh] 2 , (ppy = 2-phenylpyridine) was synthesized and characterized by IR and 1 H NMR spectroscopy as well as X-ray diffraction. The bridging carbonate ion presumably originates from the capture of CO 2 in air deduced on a series of control experiments, which may have valuable implications for the study of fixation of CO 2 . The luminescent and thermal properties of this complex were also investigated.
研究领域:
无机化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEDICINAL CHEMISTRY
·
2024
·
IF 6.8
Feng-Yang Wang,Liang-Mei Yang,Xiao-Lin Xiong,Jing Yang,Yan Yang,Jiu-Qin Tang,Lei Gao,Yuan Lu,Yuan Wang,Taotao Zou,Hong Liang,Ke-Bin Huang
Metal-based chemoimmunotherapy has recently garnered significant attention for its capacity to stimulate tumor-specific immunity beyond direct cytotoxic effects. Such effects are usually caused by ICD via the activation of DAMP signals. However, metal complexes that can elicit antitumor immune responses other than ICD have not yet been described. Herein, we report that a rhodium complex (Rh-1) triggers potent antitumor immune responses by downregulating Wnt/β-catenin signaling with subsequent activation of T lymphocyte infiltration to the tumor site. The results of mechanistic experiments suggest that ROS accumulation following Rh-1 treatment is a critical trigger of a decrease in β-catenin and enhanced secretion of CCL4, a key mediator of T cell infiltration. Through these properties, Rh-1 exerts a synergistic effect in combination with PD-1 inhibitors against tumor growth in vivo. Taken together, our work describes a promising metal-based antitumor agent with a noncanonical mode of action to sensitize tumor tissues to ICB therapy.
研究领域:
肿瘤学
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免疫学
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化学
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药理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）