- Mono- and dinuclear palladium(II) complexes containing both N-heterocyclic carbenes and tetrazole ligands as catalysts for Hiyama coupling
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Treatment of the dimeric compounds [Pd(μ-Cl)(Cl)(NHC)]2 with tetrazole ligands afforded a series of tetrazole ligand stabilized NHC-Pd complexes, including [PdCl2(IPr)(1H-tetrazole)] (1), [PdCl2(SIPr)(1H-tetrazole)] (2), [PdCl2(IPr)(1-phenyl-1H-tetrazole)] (3), [PdCl2(SIPr)(1-phenyl-1H-tetrazole)] (4), [Pd2(μ-Cl)(μ-5-phenyl-2H-tetrazole)Cl2(IPr)2] (5) and [Pd2(μ-Cl)(μ-5-pheny-2H-ltetrazole)Cl2(SIPr)2] (6) [IPr = N,N′-bis-(2,6-di(isopropyl)phenyl)imidazol-2-ylidene; SIPr = N,N′-bis-(2,6-di(isopropyl)phenyl)imidazolidin-2-ylidene]. Notably, compounds 1-4 are mononuclear NHC-Pd complexes, while compounds 5 and 6 show unprecedented μ-Cl and μ-5-phenyl-2H-tetrazole bridged dinuclear structures. The catalytic properties of the obtained NHC-Pd complexes in Hiyama coupling were initially investigated.
- Yang, Jin
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- First solid-state structures of real diorganyl phosphinous acids R 2POH (R=CF3, C2F5)
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Ring or chain? The two known phosphinous acids, (CF3) 2POH and (C2F5)2POH, reveal hydrogen-bridged aggregates in the solid state (see figure). The CF3 derivative forms helical chains, whereas the increased sterical demand of the C2F5 group leads to the formation of tetramers. The high catalytic activity of their palladium complexes (TON24500) is highlighted in the field of cross-coupling reactions. Copyright
- Bader, Julia,Berger, Raphael J. F.,Stammler, Hans-Georg,Mitzel, Norbert W.,Hoge, Berthold
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- Biogenous iron oxide-immobilized palladium catalyst for the solvent-free Suzuki-Miyaura coupling reaction
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Iron oxide produced by iron-oxidizing bacteria, Leptothrix ochracea, (biogenous iron oxide: BIO) was used as a support for immobilized palladium catalysts with organic cross-linkers. Palladium immobilized on BIO bearing imidazolium chloride delivered the desired biaryl products in sufficient yields in the Suzuki-Miyaura coupling reactions under solvent-free conditions and could be reused several times without significant loss of catalytic activity. It is shown that BIO can be exploited as a useful support for immobilization of palladium and the BIO-immobilized palladium catalyst effectively promotes the solvent-free Suzuki-Miyaura coupling reactions.
- Mandai, Kyoko,Korenaga, Toshinobu,Ema, Tadashi,Sakai, Takashi,Furutani, Mitsuaki,Hashimoto, Hideki,Takada, Jun
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- Air-stable and catalytically active phosphinous acid transition-metal complexes
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Secondary phosphane oxides R2P(O)H are most frequently used as preligands for phosphinous acid R2POH (R = alkyl, aryl) transition-metal complexes, which are very efficient catalysts for cross-coupling reactions. To investigate the influence of electron-deficient substituents on the catalytic activity, the coordination properties of bis(trifluoromethyl)-, bis(pentafluoroethyl)-, and bis[2,4-bis(trifluoromethyl) phenyl]phosphinous acid toward catalytically relevant metals, such as palladium and platinum, are studied. The novel phosphinous acid palladium complexes reveal a high catalytic activity in Heck and Suzuki cross-coupling reactions. Because of the strong dependence of these processes on the reaction conditions, a systematic solvent and base screening with 1-bromo-3-fluorobenzene and phenyl boronic acid as model reactants is performed. The most efficient solvent/base system consists of 2-propanol and potassium phosphate, providing a full conversion and a TON of around 10 000 after 20 h at room temperature with a catalyst loading of 0.01 mol % palladium. A catalyst loading of only 0.004 mol % palladium still leads to a nearly full conversion after 20 h at room temperature. During the catalytic reaction, the formation of the corresponding phosphinic acid R2P(O)OH is observed. Further investigations lead to the conclusion that palladium nanoparticles represent the catalytically active species. We also succeeded in the generation of palladium nanoparticles, which exhibit an extremely high catalytic activity in Suzuki cross-coupling reaction with TONs over 60 000 and TOFs larger than 40 000.
- Kurscheid, Boris,Belkoura, Lhoussaine,Hoge, Berthold
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- Cerium photosensitizers: Structure-function relationships and applications in photocatalytic aryl coupling reactions
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Two complete mixed-ligand series of luminescent CeIII complexes with the general formulas [(Me3Si)2NC(NiPr)2]xCeIII[N(SiMe3)2]3-x (x = 0, 1-N; x = 1, 2-N, x = 2, 3-N; x = 3, 4) and [(Me3Si)2NC(NiPr)2]xCeIII(OAr)3-x (x = 0, 1-OAr; x = 1, 2-OAr, x = 2, 3-OAr; x = 3, 4) were developed, featuring photoluminescence quantum yields up to 0.81(2) and lifetimes to 117(1) ns. Although the 4f ? 5d absorptive transitions for these complexes were all found at ca. 420 nm, their emission bands exhibited large Stokes shifts with maxima occurring at 553 nm for 1-N, 518 nm for 2-N, 508 nm for 3-N, and 459 nm for 4, featuring yellow, lime-green, green, and blue light, respectively. Combined time-dependent density functional theory (TD-DFT) calculations and spectroscopic studies suggested that the long-lived 2D excited states of these complexes corresponded to singly occupied 5d 2 orbitals. The observed difference in the Stokes shifts was attributed to the relaxation of excited states through vibrational processes facilitated by the ligands. The photochemistry of the sterically congested complex 4 was demonstrated by C-C bond forming reaction between 4-fluoroiodobenzene and benzene through an outer sphere electron transfer pathway, which expands the capabilities of cerium photosensitizers beyond our previous results that demonstrated inner sphere halogen atom abstraction reactivity by 1-N.
- Yin, Haolin,Carroll, Patrick J.,Manor, Brian C.,Anna, Jessica M.,Schelter, Eric J.
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- Coordination Properties of Perfluoroethyl- and Perfluorophenyl-Substituted Phosphonous acids, RfP(OH)2
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Phosphinic acids, RfP(O)(OH)H (Rf=CF3, C2F5, C6F5), turned out to be excellent preligands for the coordination of phosphonous acids, RfP(OH)2. Addition of C2F5P(O)(OH)H to solid PtCl2 under different reaction conditions allows the isolation and full characterization of the mononuclear complexes [ClPt{P(C2F5)(OH)O}{P(C2F5)(OH)2}2] and [Pt{P(C2F5)(OH)O}2{P(C2F5)(OH)2}] containing hydrogen-bridged [RfP(OH)O]- and RfP(OH)2 units. Further deprotonation of [Pt{P(C2F5)(OH)O}2{P(C2F5)(OH)2}2] leads to the formation of the dianionic platinate, [Pt{P(C2F5)(OH)O}4]2-, revealing four intramolecular hydrogen bridges. With PdCl2 the dinuclear complex [Pd2(μ-Cl)2{[P(C2F5)(OH)O]2H}2] was isolated and characterized. The Cl- free complex [Pd{P(C2F5)(OH)O}2{P(C2F5)(OH)2}2] was also prepared and deprotonated to the dianionic palladate, [Pd{P(C2F5)(OH)O}4]2-. Both compounds were characterized by NMR spectroscopy, IR spectroscopy, and X-ray analyses. In addition, the C6F5 derivatives [ClPt{P(C6F5)(OH)O}{P(C6F5)(OH)2}2] and [Pd2(μ-Cl)2{[P(C6F5)(OH)O]2H}2] as well as the CF3 derivative [Pd2(μ-Cl)2{[P(CF3)(OH)O]2H}2] were synthesized and fully characterized. Phosphonous acid complexes are inert towards air and moisture and can be stored for several months without decomposition. The catalytic activity of the palladium complexes in the Suzuki cross-coupling reaction between 1-bromo-3-fluorobenzene and phenyl boronic acid was demonstrated. A tautomeric equilibrium between phosphinic, RP(O)(OH)H, and phosphonous acids, RP(OH)2, is evidenced by this work (see figure). The coordination properties of phosphonous acids with electron-withdrawing CF3, C2F5, and C6F5 groups is also described.
- Allefeld, Nadine,Kurscheid, Boris,Neumann, Beate,Stammler, Hans-Georg,Ignat'Ev, Nikolai,Hoge, Berthold
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- Organocatalytic synthesis of (Het)biaryl scaffoldsviaphotoinduced intra/intermolecular C(sp2)-H arylation by 2-pyridone derivatives
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A uniqueN,O-bidentate ligand 6-oxo-1,6-dihydro-pyridone-2-carboxylic acid dimethylamide (L1) catalyzed direct C(sp2)-H (intra/intermolecular) arylation of unactivated arenes has been developed to expedite access to (Het)biaryl scaffolds under UV-irradiation at room temperature. The protocol tolerated diverse functional groups and substitution patterns, affording the target products in moderate to excellent yields. Mechanistic investigations were also carried out to better understand the reaction pathway. Furthermore, the synthetic applicability of this unified approach has been showcasedviathe construction of biologically relevant 4-quinolone, tricyclic lactam and sultam derivatives.
- Das, Tapas Kumar,Kundu, Mrinalkanti,Mondal, Biswajit,Ghosh, Prasanjit,Das, Sajal
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p. 208 - 218
(2021/12/29)
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- Efficient and Economical Preparation of Hypercrosslinked Polymers-palladium Based on Schiff Base as Recyclable Catalyst for Suzuki-Miyaura Reactions
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A novel hypercrosslinked polymer (HCP) was prepared via Friedel-Crafts alkylation reaction of Schiff base with benzene and formaldehyde dimethyl acetal (FDA) promoted by FeCl3. The HCP was then metalated with Pd(II) to form heterogeneous catalyst. The protocol featured low cost, mild conditions, readily available materials, easy separation and high yield. Physicochemical methods, including IR, N2 sorption, ICP, TGA, XPS, SEM, EDX, and TEM, were used to characterize the catalyst structure and composition. The results reveal that the heterogeneous catalyst possesses high specific surface area, large pore volume, good chemical and thermal stability, and highly dispersed palladium. The heterogeneous catalysts were applied in Suzuki-Miyaura coupling reaction to evaluate their catalytic performance. The experiments reflected that the HCPs-Pd(OAc)2 was an efficient catalyst for Suzuki-Miyaura reactions with the yield of biaryl up to 99%, while the TON could reach 2250. The reusability test showed the catalyst was easily recovered and reused for at least six times without obvious decrease in activity.
- Gao, Xiyue,Lin, Hongwei,Liu, Shasha,Luo, Qionglin,Ouyang, Yuejun,Xiang, Bailin,Xiang, Dexuan,Yao, Huan,Zhang, Li
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supporting information
p. 1879 - 1882
(2021/10/29)
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- Anchored PdCl2 on fish scale: an efficient and recyclable catalyst for Suzuki coupling reaction in aqueous media
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PdCl2 anchored on fish scale (FS) complex were intended to a heterogeneous catalyst for ligand-free Suzuki coupling reaction in aqueous media. The catalyst FS-PdCl2 was characterized by FT-IR, powder XRD, XPS and SEM. FS-PdCl2 complex has been successfully implemented for Suzuki coupling reactions of various halogenated aromatics with arylboronic acid to provide the corresponding biaryl compounds under environmentally friendly conditions (40 °C, water solvent). Moreover, the efficient catalyst shows excellent stability and recyclability, and its catalytic activity without any decrease after 8 times consecutive reused.
- Yang, Quanlu,Yang, Fawang,Zhang, Ying,Hou, Juanjuan,Li, Jiankun,Cheng, Jinkui,Wu, Shang,Zhan, Huiying,Zhang, Xinghui,Shi, Haixiong
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supporting information
(2020/12/25)
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- Sulfonate Versus Sulfonate: Nickel and Palladium Multimetallic Cross-Electrophile Coupling of Aryl Triflates with Aryl Tosylates
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While phenols are frequent and convenient aryl sources in cross-coupling, typically as sulfonate esters, the direct cross-Ullmann coupling of two different sulfonate esters is unknown. We report here a general solution to this challenge catalyzed by a combination of Ni and Pd with Zn reductant and LiBr as an additive. The reaction has broad scope, as demonstrated in 33 examples (65% ± 11% average yield). Mechanistic studies show that Pd strongly prefers the aryl triflate, the Ni catalyst has a small preference for the aryl tosylate, aryl transfer between catalysts is mediated by Zn, and Pd improves yields by consuming arylzinc intermediates.
- Kang, Kai,Huang, Liangbin,Weix, Daniel J.
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supporting information
p. 10634 - 10640
(2020/07/08)
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- Highly Active Heterogeneous PdCl2/MOF Catalyst for Suzuki–Miyaura Cross-Coupling Reactions of Aryl Chloride
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The exploration of highly efficient Pd/MOF heterogeneous catalyst system for the Suzuki–Miyaura cross-coupling (SMC) reactions of aryl chlorides is still challenging. Herein, a PdCl2/UiO-67-bpydc was successfully synthesized by immobilizing a low amount of PdCl2 onto the zirconium-based MOF (UiO-67-bpydc). PdCl2/UiO-67-bpydc showed excellent catalytic performance and good recycle ability for the SMC reaction of aryl chlorides under an ambient condition. Furthermore, PdCl2/UiO-67-bpydc retains the high catalytic activity even after five cycles, and exhibited excellent substrate size selectivity.
- Gong, Xue-Fang,Zhang, Ling-Yan,Zhang, Hui-Xin,Cui, Yu-Meng,Jin, Fen-Chun,Liu, Yu,Zhai, Yu-Feng,Li, Jin-Heng,Liu, Gui-Yan,Zeng, Yong-Fei
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p. 1336 - 1341
(2020/07/06)
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- Palladium supported on triazolyl-functionalized hypercrosslinked polymers as a recyclable catalyst for Suzuki-Miyaura coupling reactions
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A novel hypercrosslinked polymers-palladium (HCPs-Pd) catalyst was successfully preparedviathe external cross-linking reactions of substituted 1,2,3-triazoles with benzene and formaldehyde dimethyl acetal. The preparation of HCPs-Pd has the advantages of low cost, mild conditions, simple procedure, easy separation and high yield. The catalyst structure and composition were characterized by N2sorption, TGA, FT-IR, SEM, EDX, TEM, XPS and ICP-AES. The HCPs were found to possess high specific surface area, large micropore volume, chemical and thermal stability, low skeletal bone density and good dispersion for palladium chloride. The catalytic performance of HCPs-Pd was evaluated in Suzuki-Miyaura coupling reactions. The results show that HCPs-Pd is a highly active catalyst for the Suzuki-Miyaura coupling reaction in H2O/EtOH solvent with TON numbers up to 1.66 × 104. The yield of biaryls reached 99%. In this reaction, the catalyst was easily recovered and reused six times without a significant decrease in activity.
- Lin, Hongwei,Liu, Cijie,Liu, Shasha,Luo, Qionglin,Ouyang, Yuejun,Shu, You,Xiang, Dexuan,Xu, Wei,Zheng, Lijuan
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p. 17123 - 17128
(2020/05/18)
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- Palladium Immobilized on 2,2′-Dipyridyl-Based Hypercrosslinked Polymers as a Heterogeneous Catalyst for Suzuki–Miyaura Reaction and Heck Reaction
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Abstract: 2,2′-Bipyridine was successfully integrated into the skeleton of hypercrosslinked polymers networks (HCPs-bipy) via Friedel–Crafts reaction and Scholl coupling reaction, and PdCl2 was locked in this network polymers by coordination with pyridine motif. The preparation of HCPs-bipy has the advantages of low cost, mild conditions, easy separation and high yield. FT-IR, TGA, N2 sorption, ICP, XPS, SEM, EDX and TEM was employed to characterize the structure and composition of the heterogeneous catalysts. The result indicates that HCPs-bipy-Pd possess high specific surface areas, large microporous volume, thermal stability, and highly dispersion of palladium species. HCPs-bipy-Pd can be applied in Suzuki–Miyaura reactions and Heck reactions as robust heterogeneous catalyst to afford high yield. The reusability test demonstrates that HCPs-bipy-Pd could be recovered and reused for at least five times without losing catalytic activity. Graphic Abstract: [Figure not available: see fulltext.].
- Liu, Cijie,Xu, Wei,Xiang, Dexuan,Luo, Qionglin,Zeng, Shunqin,Zheng, Lijuan,Tan, Yujie,Ouyang, Yuejun,Lin, Hongwei
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p. 2558 - 2565
(2020/03/23)
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- Small organic molecules with tailored structures: Initiators in the transition-metal-free C-H arylation of unactivated arenes
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Simple, small organic molecules containing nitrogen and oxygen atoms in their structures have been disclosed to catalyze transition-metal-free C-H arylation of unactivated arenes with aryl iodides in the presence of tBuOK. In this article, an optimized catalytically active molecule, (2-(methylamino)phenyl)methanol, was designed. A broad range of aryl iodides could be converted into the corresponding arylated products at 100 °C over 24 h with good to excellent yields. Mechanistic experiments verified that radicals participated in this catalytic transformation and that the cleavage of the aromatic C-H bond was not the rate determining step. A K+ capture experiment by 18-crown-6 emphasized the significance of the cation species of the strong base. Fourier transform infrared spectroscopy proved that the catalytic system was activated by the hydrogen bonds between small organic molecules and tBuOK. Also, a clear mechanism was proposed. This transition-metal-free method affords a promising system for efficient and inexpensive synthesis of biaryls via a user-friendly approach, as confirmed by scale-up experiments.
- Chen, Suqing,Chen, Wenjun,Chen, Yu,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong
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p. 14500 - 14509
(2020/04/27)
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- Organocatalyst in Direct C(sp2)-H Arylation of Unactivated Arenes: [1-(2-Hydroxyethyl)-piperazine]-Catalyzed Inter-/Intra-molecular C-H Bond Activation
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This article describes the identification of 1-(2-hydroxyethyl)-piperazine as a new, cost-effective, highly efficient organocatalyst, which promotes both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in the presence of potassium tert-butoxide. While the inter-molecular C-H arylation of unactivated benzenes with aryl halides (Ar-X; X = I, Br, Cl) toward biaryl syntheses underwent smoothly in the presence of only 10 mol percent organocatalyst, the intra-molecular C-H arylation catalytic system composed of 40 mol percent each of the catalyst and the additive (4-dimethylaminopyridine (DMAP)). The novel catalyst was also able to perform both inter- A nd intra-molecular direct arylations simultaneously in a single pot. The mechanistic studies confirmed the involvement of aryl radical anions and proceeded via a single-electron-transfer (SET) mechanism. The large substrate scope, high functional group tolerance, competition experiments, gram-scale synthesis, and kinetic studies further highlight the importance and versatile nature of the methodology as well as the compatibility of the new catalyst. To the best of our knowledge, this is the first report on any organocatalyst that reported detailed investigations of both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in a single representation.
- Yadav, Lalit,Tiwari, Mohit K.,Shyamlal, Bharti Rajesh Kumar,Chaudhary, Sandeep
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p. 8121 - 8141
(2020/07/16)
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- Immobilized Pd on Eggshell Membrane: A powerful and recyclable catalyst for Suzuki and Heck cross-coupling reactions in water
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A stable heterogeneous palladium catalysts, the waste eggshell membrane (ESM) anchored Pd complex, was synthesized by a simple and green technique. The catalyst obtained can display an outstanding catalytic activity for Suzuki and Heck coupling reactions in water media. The reactions of various aryl halides with aryl boronic acids and terminal alkenes provided the corresponding products in moderate to excellent yields. More importantly, this novel and efficient catalyst with high stability can be easily reused for at least twelve times with no decrease of the catalytic activity, performing an endurable and wide tolerance of the substrates. Facile synthesis, high catalytic activity, and recyclability make these catalysts interesting for further studies.
- Wu, Shang,Jiang, Hongyan,Zhang, Hong,Zhao, Lianbiao,Yuan, Peilin,Zhang, Ying,Su, Qiong,Wang, Yanbin,Wu, Lan,Yang, Quanlu
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- Palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides by carbon-nitrogen bond activation
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Palladium-catalyzed Suzuki-Miyaura cross-coupling or aryl halides is widely employed in the synthesis of many important molecules in synthetic chemistry, including pharmaceuticals, polymers and functional materials. Herein, we disclose the first palladium-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of amides for the synthesis of biaryls through the selective activation of the N-C(O) bond of amides. This new method relies on the precise sequence engineering of the catalytic cycle, wherein decarbonylation occurs prior to the transmetallation step. The reaction is compatible with a wide range of boronic acids and amides, providing valuable biaryls in high yields (>60 examples). DFT studies support a mechanism involving oxidative addition, decarbonylation and transmetallation and provide insight into high N-C(O) bond activation selectivity. Most crucially, the reaction establishes the use of palladium catalysis in the biaryl Suzuki-Miyaura cross-coupling of the amide bond and should enable the design of a wide variety of cross-coupling methods in which palladium rivals the traditional biaryl synthesis from aryl halides and pseudohalides.
- Zhou, Tongliang,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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p. 9865 - 9871
(2019/11/11)
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- Cobalt-Catalyzed Cross-Coupling Reactions of Aryl Triflates and Lithium Arylborates
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A catalyst system comprising CoCl2/IAd·HBF4 enables the Suzuki-Miyaura cross-coupling reaction of a broad range of aryl triflates and arylboronic esters that are activated by n-butyllithium.
- Duong, Hung A.,Yeow, Zong-Han,Tiong, Yong-Lun,Mohamad Kamal, Nur Haidah Binte,Wu, Wenqin
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p. 12686 - 12691
(2019/10/11)
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- A Highly Active Catalyst System for Suzuki-Miyaura Coupling of Aryl Chlorides
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A series of new Pd(II) complexes with simple structures were designed and synthesized for Suzuki-Miyaura coupling reactions of aryl chlorides. The new Pd(II) complexes contain bidentate amine ligands, and their structures were characterized by single-crystal X-ray diffraction. They are highly efficient for Suzuki-Miyaura coupling reactions of aryl chlorides with low catalyst loadings (0.01 mol %) in aqueous media at room temperature. Two possible reaction pathways involving a PdII/0/II and a PdII/IV/II catalytic cycle are proposed, and the mechanism was further investigated using density functional theory (DFT) calculations.
- Liu, Guiyan,Han, Fangwai,Liu, Chengxin,Wu, Hongli,Zeng, Yongfei,Zhu, Rongjiao,Yu, Xia,Rao, Shuang,Huang, Genping,Wang, Jianhui
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p. 1459 - 1467
(2019/03/19)
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- Palladium catalyst immobilized on functionalized microporous organic polymers for C-C coupling reactions
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Two microporous organic polymer immobilized palladium (MOP-Pd) catalysts were prepared from benzene and 1,10-phenanthroline by Scholl coupling reaction and Friedel-Crafts reaction, respectively. The structure and composition of the catalyst were characterized by FT-IR, TGA, N2 sorption, SEM, TEM, ICP-AES and XPS. MOP-Pd catalysts were found to possess high specific surface areas, large pore volume and low skeletal bone density. Moreover, the immobilized catalyst also had advantages, such as readily available raw materials, chemical and thermal stability, and low synthetic cost. The Pd catalyst is an effective heterogeneous catalyst for carbon-carbon (C-C) coupling reactions, such as the Heck reaction and Suzuki-Miyaura reaction, affording good to high yields. In these reactions, the catalyst was easily recovered and reused five times without significant activity loss.
- Xu, Wei,Liu, Cijie,Xiang, Dexuan,Luo, Qionglin,Shu, You,Lin, Hongwei,Hu, Yangjian,Zhang, Zaixing,Ouyang, Yuejun
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p. 34595 - 34600
(2019/11/11)
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- Palladium immobilized on functionalized hypercrosslinked polymers: A highly active and recyclable catalyst for Suzuki-Miyaura coupling reactions in water
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Heterogeneous catalysts have shown advantages such as high stability, good recyclability and easy separation from reactants over homogeneous catalysts in recent years. In this paper, three pyridine-functionalized N-heterocyclic carbene-palladium complexes (HCP-Pd) were successfully synthesized via a simple external cross-linking reaction. In each catalyst (i.e., complex), palladium (Pd) was immobilized on the hypercrosslinked polymer (HCP) via formation of a six-membered ring by Pd2+ and the bidentate ligands of NHC and pyridine. The structure and composition of HCP-Pd were characterized by SEM, TEM, N2 sorption, FT-IR, TGA and XPS. The catalytic performances of these catalysts in a Suzuki-Miyaura coupling reaction were also studied. The results prove that HCP-Pd is a very effective heterogeneous catalyst for the Suzuki-Miyaura coupling reaction of various aryl halides with aryl boronic acid in an aqueous medium under mild conditions.
- Liu, Xi,Xu, Wei,Xiang, Dexuan,Zhang, Zaixing,Chen, Dizhao,Hu, Yangjian,Li, Yuanxiang,Ouyang, Yuejun,Lin, Hongwei
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supporting information
p. 12206 - 12210
(2019/08/12)
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- Highly active NHC-Pd(ii) complexes for cross coupling of aryl chlorides and arylboronic acids: An investigation of the effect of remote bulky groups
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A series of palladium(ii) complexes bearing remote bulky ligands were synthesized and characterized. Their catalytic activity for Suzuki-Miyaura cross-coupling reactions and the effect of remote bulky groups were investigated. These new palladium complexes are highly efficient for the Suzuki-Miyaura cross-coupling reactions of aryl chlorides and arylboronic acids with low catalyst loadings (0.05 mol%) at room temperature in air.
- Han, Fangwai,Xu, Ying,Zhu, Rongjiao,Liu, Guiyan,Chen, Chen,Wang, Jianhui
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p. 7422 - 7427
(2018/05/04)
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- Graphene oxide-phenalenyl composite: transition metal-free recyclable and catalytic C-H functionalization
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An efficient route towards a heterogeneous transition metal-free catalytic C-H functionalization using a covalently linked graphene oxide-phenalenyl conjugate is described herein (28 examples, which include a core of some biologically relevant biaryl and hetero-biaryls). It is an environmentally benign, economical and heterogeneous platform, whose catalytic activity can easily be regenerated through a simple washing-drying technique and the catalytic activity can be retained even after 10 cycles.
- Singh, Bhagat,Paira, Rupankar,Biswas, Goutam,Shaw, Bikash Kumar,Mandal, Swadhin K.
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supporting information
p. 13220 - 13223
(2018/12/10)
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- Alkylimidazole-Based Phosphines as Efficient Ligands for Palladium-Catalyzed Suzuki Reactions
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Two series of alkylimidazole-based phosphines were conveniently synthesized in one step from the corresponding alkylimidazole by selective deprotonation and quenching with chlorodiphenylphosphine. The novel ligands are easily tunable and exhibit good-to-excellent performance in the palladium-catalyzed Suzuki coupling reaction.
- Chen, Ting,Guan, Jin Tao,Zhang, Zhi Yong,Chen, Jing Jing,Liu, Fengyan,Liu, Xiaopei
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p. 551 - 555
(2017/12/26)
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- Series high-containing sterically hindered group modified Pd - PEPPSI - NHC complexes and use thereof (by machine translation)
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The present invention discloses a series of high-containing sterically hindered group modified Pd - PEPPSI - NHC complex (and complex single crystal) and use. The invention relates to a Pd - PEPPSI - NHC complex is containing high sterically hindered group modified N - heterocyclic carbene ligand, at the same time still applies pyridine or its derivatives as the auxiliary ligand. The invention containing high sterically hindered group modified Pd - PEPPSI - NHC complex (and complex single crystal) has higher stability, it also can be used as a catalyst high-efficiency catalytic chlorinated aromatic hydrocarbon aryl boric acid and Suzuki - Miyaura coupling reaction. (by machine translation)
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Page/Page column 10
(2018/09/13)
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- PRODUCTION METHOD OF COUPLING REACTION PRODUCT OF ORGANIC COMPOUND HAVING LEAVING GROUP WITH ORGANOBORON COMPOUND
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PROBLEM TO BE SOLVED: To provide a production method with which a coupling product of the Suzuki-Miyaura cross-coupling reaction can be obtained without using any special ligand, with a practically available yield, and with an amount of catalyst of order of mol ppm. SOLUTION: In a production method, a coupling product is produced by making an organic compound having a leaving group selected from bromine atom, iodine atom, methanesulfonyloxy group, and trifluoromethanesulfonyloxy group react with an organoboron compound in the presence of a catalyst, a base and a solvent, in which the catalyst is a palladium salt with an amount of 10 mol ppm or less, the base is a carbonate, and the solvent is a mixed solvent including ethanol or isopropanol and water, and the reaction is carried out in an oxygen-containing gaseous atmosphere. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0025-0027
(2018/05/24)
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- Direct arylation of inactivated benzene with aryl acyl peroxides toward biaryls
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A direct arylation of inactivated benzene with acyl peroxides was developed, affording biaryls in good to excellent yields. This transformation underwent a radical pathway under metal-free, base-free and additive-free conditions with good functional group compatibility.
- Pan, Changduo,Zhu, Jiawei,Chen, Rongzhen,Yu, Jin-Tao
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supporting information
p. 6467 - 6469
(2017/08/16)
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- Highly active palladium catalysts containing a 1,10-phenanthroline analogue N-heterocyclic carbene for room temperature Suzuki-Miyaura coupling reactions of aryl chlorides with arylboronic acids in aqueous media
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Two new palladium (II) complexes containing a 1,10-phenanthroline analogue N-heterocyclic carbene (NHC) have been synthesized. The complexes were characterized by 1H and 13C NMR spectroscopy and elemental analysis and their structures were determined by single-crystal X-ray diffraction. The NHC-palladium complexes were employed as catalysts for Suzuki-Miyaura coupling reactions of aryl chlorides with arylboronic acids in aqueous media at room temperature. The cross-coupling reactions were highly efficient with low catalysts loadings.
- Liu, Guiyan,Liu, Chengxin,Han, Fangwai,Wang, Zhongliang,Wang, Jianhui
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supporting information
p. 726 - 731
(2017/03/31)
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- N-Doped porous carbon nanotubes: Synthesis and application in catalysis
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Uniform N-doped carbon nanotubes were obtained for the first time via a morphology-preserving thermal transformation of organic polymer nanotubes without any additional templates. These carbon nanotubes acted as a superior metal-free carbon catalyst for C-H arylation of benzene, reductive hydrogen atom transfer and oxidation reactions.
- Yang, Zhenzhen,Liu, Zhenghui,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Wang, Huan,Ji, Guipeng,Chen, Yu,Liu, Xinwei,Liu, Zhimin
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supporting information
p. 929 - 932
(2017/01/17)
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- METHOD FOR AROMATIC FLUORINATION
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Disclosed is a fluorination method comprising providing an aryl fluorosuifonate and a fluorinating reagent to a reaction mixture; and reacting the aryl fluorosuifonate and the fluorinating reagent to provide a fluorinated aryl species. Also disclosed is a fluorination method comprising providing, a salt comprising a cation and an aryloxyiate, and SO2F2 to a reaction mixture; reacting the SO2F2 and the ammonium salt to provide a fluorinated aryl species. Further disclosed a fluorination method comprising providing a compound having the structure Ar-OH to a reaction mixture; where A is an aryl or heteroaryl; providing SO2F2 to the reaction mixture; providing a fluorinating reagent to the reaction mixture; reacting the SO2F2, the fluorinating reagent and the compound having the structure Ar-OH to provide a fluorinated aryl species having the structure Ar-F.
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Paragraph 0047-0049
(2017/12/18)
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- ortho-C?H Arylation of Benzoic Acids with Aryl Bromides and Chlorides Catalyzed by Ruthenium
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A system consisting of catalytic amounts of [(p-cym)RuCl2]2/PEt3?HBF4, K2CO3as the base, and NMP as the solvent efficiently mediates the ortho-C?H arylation of benzoic acids with aryl bromides at 100 °C. Replacing the phosphine ligand with the amino acid dl-pipecolinic acid enables the analogous transformation with aryl chlorides. The key advantage of this broadly applicable transformation is the use of an inexpensive ruthenium catalyst in combination with simple carboxylates as directing groups, which can either be tracelessly removed or used as anchor points for decarboxylative ipso substitutions.
- Biafora, Agostino,Krause, Thilo,Hackenberger, Dagmar,Belitz, Florian,Goo?en, Lukas J.
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supporting information
p. 14752 - 14755
(2016/11/23)
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- An Indefinitely Air-Stable σ-NiII Precatalyst for Quantitative Cross-Coupling of Unreactive Aryl Halides and Mesylates with Aryl Neopentylglycolboronates
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Three classes of Ni precatalysts based on π-NiII, π-Ni0 and σ-NiII complexes have been elaborated and employed in different laboratories for the functionalization and cross-coupling of otherwise inert aryl C-O, C-Cl, and C-F electrophiles. Various Ni precatalysts, ligands, boron sources, and reaction conditions that were developed in various research groups, necessitated the selection of the most suitable conditions for desired cross-coupling partners. Here a universal, bench-stable, easily prepared NiIICl(1-naphthyl)(PCy3)2/PCy3 σ-complex, for efficient and quantitative cross-coupling of aryl chlorides, bromides, iodides, mesylates, and fluorides with aryl neopentylglycolboronates is reported. This precatalyst will most probably help to advance the applications of Ni catalysis in organic, supramolecular, and macromolecular synthesis and will provide an easier access to the selection of reaction conditions for various transformations.
- Malineni, Jagadeesh,Jezorek, Ryan L.,Zhang, Na,Percec, Virgil
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supporting information
p. 2795 - 2807
(2016/08/31)
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- Newly-generated Al(OH)3-supported Pd nanoparticles-catalyzed Stille and Kumada coupling reactions of diazonium salts, (Het)aryl chlorides
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A ligand-free Pd/Al(OH)3 nano-catalyst which is prepared by one-pot three-component method using Pd(PPh3)4, tetra (ethylene glycol), and aluminum tri-sec-butoxide exhibits excellent catalytic activity in Stille cross-couplings of (Het)aryl chlorides, arenediazonium tetrafluoroborate salts with phenyltributylstannane, respectively, and Kumada couplings of (Het)aryl chlorides with various Grignard reagents. More importantly, these two processes show excellent functional group compatibility with moderate to good yields and they are also versatile with respect to not only (Het)aryl chlorides, but also diazonium salts, and heteroaryl Grignard reagents. The nano-catalyst could also be recycled and reused 5 times without loss of activity and decrease of yield.
- Li, Xing,Zhu, Tingting,Shao, Zhongqi,Li, Yingjun,Chang, Honghong,Gao, Wenchao,Zhang, Yongli,Wei, Wenlong
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supporting information
p. 69 - 75
(2015/12/23)
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- Polyureas derived from CO2 and diamines: highly efficient catalysts for C-H arylation of benzene
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Polyureas derived from CO2 and diamines were effective for C-H arylation of benzene in the presence of t-BuOK, producing biaryl products with various substituents in high yields up to 97%. Dual-activation of K+ and t-BuO-, and π,π-stacking interaction between the substrate and the polymer backbone may account for the superior activity.
- Liu, Zhenghui,Yang, Zhenzhen,Hao, Leiduan,Liu, Xinwei,Zhang, Hongye,Yu, Bo,Liu, Zhimin
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supporting information
p. 51 - 55
(2016/12/30)
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- Ligand-promoted oxidative cross-coupling of aryl boronic acids and aryl silanes by palladium catalysis
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The first cross-coupling reaction between aryl silanes and aryl boronic acids is described. This transformation represents one of the very few examples of coupling reactions between two nucleophilic organometallic reagents and provides a new method for the formation of biaryl compounds. The successful development of this reaction was enabled by the use of commercially available 2,2-bis(diphenylphosphino)-1,1-binaphthyl (BINAP) as the ligand. A small amount of BINAP (3 mol %) was sufficient to suppress the formation of the homocoupling products, and the reaction yielded the cross-coupling products with high selectivity under mild conditions, even when the ratio of the two coupling partners was 1:1.
- Yu, Jingxun,Liu, Jun,Shi, Guangfa,Shao, Changdong,Zhang, Yanghui
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supporting information
p. 4079 - 4082
(2015/03/30)
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- Electrochemical synthesis of Pd nano particles on pencil- graphite and application for suzuki coupling reactions
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Synthesis of Pd nano particles by electrochemical deposition on pencil graphite has been carried out. Catalytic activity of these nanoparticles was tested for Suzuki coupling reactions. The heterogeneous catalyst was synthesized in 10 s and without use of hazardous reducing reagent. The catalyst showed excellent catalytic performance towards Suzuki cross coupling reaction in aqueous medium. The catalyst was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy dispersive X-ray analysis, thermo gravimetric analysis, inductively coupled plasma and EDX mapping techniques. Pd nano particles were found to have monodispersed nature with average particle size of 9-10 nm in diameter. The developed catalyst can be recycled up to five cycles without significant decrease in the product yield.
- Balsane, Kishor E.,Shelkar, Radheshyam S.,Nagarkar, Jayashree M.
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p. 1817 - 1824
(2019/11/28)
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- Palladium(II) on functionalized NiFe2O4: An efficient and recyclable phosphine-free heterogeneous catalyst for suzuki coupling reaction
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Superparamagnetic NiFe2O4 catalyst immobilized palladium(II) has been synthesized using a microemulsion method and functionalized with Schiff-base group to form an immobilized bidentate ligand. The catalyst was characterized by multiple analytical techniques. The immobilized palladium complex was used in EtOH/water under aerobic conditions. The catalyst is applicable for various substrates and easily separable. The as-prepared catalyst was reused up to five runs with slight decrease in catalytic activity. Graphical Abstract: [Figure not available: see fulltext.]
- Singh, Abhilash S.,Shelkar, Radheshyam S.,Nagarkar, Jayashree M.
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p. 723 - 730
(2015/08/04)
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- Ligand-controlled chemoselectivity in potassium tert-amylate-promoted direct C-H arylation of unactivated benzene with aryl halides
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Direct C-H arylation of unactivated benzene with aryl halides under various simple ligands (EDA, DMEDA, ethylene glycol, etc.) in the presence of potassium tert-amylate (t-AmOK) base at mild temperature (80 °C) have been developed. This transition-metal-free radical cross-coupling offers an efficient way to synthesize various biaryls in good yields through base-promoted homolytic aromatic substitution. And mechanistic investigations have provided insight into the chemoselectivity of couplings between haloiodobenzenes and benzene and showed that phenanthroline and its derivatives not only initiate these radical reactions like most of other ligands (EDA, DMEDA, ethylene glycol, etc.), but also participate in the electron transfer process of biaryl radical anion intermediates.
- Liu, Wei,Xu, Lige
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p. 4974 - 4981
(2015/06/25)
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- A green approach for the decoration of Pd nanoparticles on graphene nanosheets: An in situ process for the reduction of C-C double bonds and a reusable catalyst for the Suzuki cross-coupling reaction
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A new strategy for in situ synthesis of palladium nanoparticles (Pd NPs) decorated on reduced graphene oxide (rGO) nanosheets with controlled size and shape is reported. This strategy was designed as three processes in one pot, namely, (a) reduction of graphene oxide, (b) formation of Pd NPs on the rGO nanosheets and (c) simultaneous reduction of olefin. In this synthesis process, a hydrogen atmosphere was used to develop the Pd NPs-rGO nanocatalyst, which is reusable and easily separable. The influence of the size and morphology of the Pd-rGO-H2 catalyst on the catalytic activity in the Suzuki cross-coupling reaction was investigated by comparing with other catalysts, Pd-rGO-As and Pd-rGO-Gl, and they were synthesized by different reducing agents, ascorbic acid and glucose, respectively. The catalysts were characterized by electron microscopy (HRTEM, SEM), FT-IR, XRD and XPS. The Pd-rGO-H2 catalyst was found to possess excellent catalytic activity and recyclability in the Suzuki cross-coupling reaction under mild reaction conditions.
- Hussain, Najrul,Borah, Ashwini,Darabdhara, Gitashree,Gogoi, Pranjal,Azhagan, Vedi Kuyil,Shelke, Manjusha V.,Das, Manash R.
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p. 6631 - 6641
(2015/08/06)
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- Catalytic activity of 1-methylimidazole-based phosphine ligands in the palladium-catalyzed Suzuki coupling reaction
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The catalytic activities of three N-methylimidazole-based phosphine ligands in the Suzuki coupling reaction were tested using PdCl2 as the catalyst. The results showed all three phosphine ligands exhibited excellent activity towards the Suzuki reaction, and the catalytic activity decreased with increasing number of imidazole groups.
- Guan, Jin Tao,Song, Xiao Ming,Zhang, Zhi Yong,Wei, Ben Mei,Dai, Zhi Qun
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- Nano Pd-Fe3O4@Alg beads: As an efficient and magnetically separable catalyst for Suzuki, Heck and Buchwald-Hartwig coupling reactions
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Catalytic processes are the backbone of many chemical industries. In a comparative study of various heterogeneous catalytic systems, we report efficient and magnetically separable nano Pd-Fe3O4@Alg beads as catalysts for Suzuki, Heck and Buchwald-Hartwig coupling reactions. This catalyst was characterized by SEM, TEM, HRTEM, XRD, EDAX, FT-IR, VSM, DSC-TGA, BET, and UV-Visible spectroscopy. This heterogeneous catalyst showed high catalytic activity and stability for C-C and C-N bond forming coupling reactions with excellent product yield under ligand free conditions. The beads of nano Pd-Fe3O4@Alg can be separated from the reaction mixture by an external magnet and reused for several successive cycles with no appreciable loss in the catalytic activity. The Suzuki and Heck coupling reactions in aqueous medium are greener routes, which is an added advantage of this protocol. This journal is
- Shelkar, Radheshyam S.,Gund, Sitaram H.,Nagarkar, Jayashree M.
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p. 53387 - 53396
(2015/02/05)
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- Visible-light photoredox in homolytic aromatic substitution: Direct arylation of arenes with aryl Halides
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Direct arylation of unactivated arenes or heteroarenes with aryl halides could be carried out in the presence of potassium tert-butoxide and dimethyl sulfoxide under visible-light irradiation. Ir(ppy)3 was found to be an effective photoredox catalyst for this reaction. The reactions of aryl iodides occurred at room temperature. Elevated temperature was required for aryl bromides. Homolytic aromatic substitution was proposed to be the operative reaction pathway.
- Cheng, Yannan,Gu, Xiangyong,Li, Pixu
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supporting information
p. 2664 - 2667
(2013/07/11)
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- Platinum-catalyzed C-H arylation of simple arenes
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This report describes the Na2PtCl4 catalyzed C-H arylation of arene substrates with diaryliodonium salts. The site selectivity of these reactions is predominantly controlled by steric factors. Remarkably, Na2PtCl4-catalyzed naphthalene arylation proceeds with opposite site selectivity compared to that obtained with Na2PdCl 4 as the catalyst. Preliminary mechanistic studies provide evidence for a PtII/PtIV catalytic cycle involving rate-limiting C-C bond-forming reductive elimination.
- Wagner, Anna M.,Hickman, Amanda J.,Sanford, Melanie S.
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supporting information
p. 15710 - 15713
(2013/11/06)
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- Palladium-catalyzed Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids
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Readily available NHC-Pd(ii)-Mp complexes 2 showed efficient catalytic activity toward the Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids or potassium phenyltrifluoroborate, giving the expected coupling products in good to high yields.
- Wang, Zhan-Yong,Ma, Qin-Na,Li, Ren-Hao,Shao, Li-Xiong
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p. 7899 - 7906
(2013/11/19)
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- Pd-catalyzed cross-coupling reactions of arenediazonium salts with arylsilanes and aryltrifluoroborates in water
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Pd-catalyzed cross-coupling reactions of various arenediazonium salts with ArSi(OR)3 and KArBF3 have been achieved in good to excellent yields under simple aerobic conditions in water at room temperature. The functional group tolerance makes these transformations as attractive alternatives to the traditional cross-coupling approaches. Furthermore, the sequence can also be performed in a one-pot domino process, omitting the isolation of the intermediate arenediazonium salt.
- Cheng, Kai,Zhao, Baoli,Hu, Sai,Zhang, Xian-Man,Qi, Chenze
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supporting information
p. 6211 - 6214
(2013/10/22)
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- Palladium-catalyzed Hiyama-type cross-coupling reactions of arenesulfinates with organosilanes
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Palladium-catalyzed Hiyama-type cross-coupling reactions of various arenesulfinates with organosilanes were achieved in good to excellent yields under aerobic conditions at 70 °C. Fluoride is essential, and tetrabutylammonium fluoride (TBAF) was shown to
- Cheng, Kai,Hu, Sai,Zhao, Baoli,Zhang, Xian-Man,Qi, Chenze
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p. 5022 - 5025
(2013/06/27)
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- Novel bisimidazolium pincers as low loading ligands for in situ palladium-catalyzed Suzuki-Miyaura reaction in the ambient atmosphere
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A series of novel triazinonide-bridged bisimidazolium pincers were easily synthesized by quaternization of functionalized N-phenylimidazoles with highly reactive cyanuric chloride under mild conditions. The pincer 3c was proven to be a very efficient ligand for in situ Pd-catalyzed Suzuki-Miyaura reaction with ppm-level catalyst loading.
- Gao, Chao,Zhou, Hongjun,Wei, Siping,Zhao, Yinsong,You, Jingsong,Gao, Ge
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supporting information
p. 1127 - 1129
(2013/03/13)
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- Proline catalyzes direct C-H arylations of unactivated arenes
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Several amino acids were tested to catalyze the transition-metal-free direct C-H arylation of unactivated benzene derivatives. Among them, proline was found to be an excellent catalyst for the cross-coupling between aryl halides and unactivated arenes. The reaction presumably involves an aryl radical anion as the intermediate based on several experiments. The reaction using this catalyst system offers an option toward establishing an environmentally benign and cost-effective route to biaryls.
- Tanimoro, Kouichi,Ueno, Minoru,Takeda, Kazutaka,Kirihata, Mitsunori,Tanimori, Shinji
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p. 7844 - 7849
(2013/01/15)
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- Cine substitution of arenes using the aryl carbamate as a removable directing group
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An efficient and controlled means to achieve a rare cine substitution of arenes is reported. The methodology relies on the strategic use of aryl O-carbamates as readily removable directing groups for arene functionalization. The removal of aryl carbamates is achieved by employing an air-stable Ni(II) precatalyst, along with an inexpensive reducing agent, to give synthetically useful yields across a range of substrates. The net cine substitution process offers a new strategy for analogue synthesis, which complements the well-established logic for achieving arene functionalization by ipso substitution.
- Mesganaw, Tehetena,Fine Nathel, Noah F.,Garg, Neil K.
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p. 2918 - 2921
(2012/07/28)
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- Biphenyl-based diaminophosphine oxides as air-stable preligands for the nickel-catalyzed kumada-tamao-corriu coupling of deactivated aryl chlorides, fluorides, and tosylates
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A cooperative couple: Cooperative bimetallic activation of C-F and C-O bonds gave rise to easy coupling with aryl fluorides and tosylates. Novel air- and moisture-stable diaminophosphine oxides derived from 1,1′-biphenyl-2, 2′-diamine proved to be versatile preligands for the nickel-catalyzed cross-coupling of aryl Grignard reagents with a variety of deactivated aryl chlorides, fluorides, and tosylates (see scheme). Copyright
- Jin, Zhong,Li, Yan-Jing,Ma, Yong-Qiang,Qiu, Ling-Ling,Fang, Jian-Xin
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supporting information; experimental part
p. 446 - 450
(2012/02/15)
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- TBAF-assisted palladium-catalyzed Suzuki reaction in water under the ligand and base-free conditions
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Tetrabutyl ammonium fluoride (abbreviated as TBAF)-assisted palladium-catalyzed Suzuki reaction in neat water has been demonstrated under the ligand and base-free conditions. The cross-coupling of aryl or heteroaryl bromides with arylboronic acids generated the corresponding products in good to excellent yields in the presence of low concentration of palladium acetate in combination with TBAF under air.
- Wu, Xiang-Mei,Gu, Yong-Bing
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experimental part
p. 396 - 400
(2012/10/07)
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