- A Ni0 σ-Borane Complex Bearing a Rigid Bidentate Borane/Phosphine Ligand: Boryl Complex Formation by Oxidative Dehydrochloroborylation and Catalytic Activity for Ethylene Polymerization
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While of interest, synthetically feasible access to boryl ligands and complexes remains limited, meaning such complexes remain underexploited in catalysis. For bidentate boryl ligands, oxidative addition of boranes to low-valent IrI or Pt0 are the only examples yet reported. As part of our interest in developing improved group 10 ethylene polymerization catalysts, we present here an optimized synthesis of a novel, rigid borane/phosphine ligand and its Ni0 σ-borane complex. From the latter, an unprecedented oxidative dehydrochloroborylation, to give a NiII boryl complex, was achieved. Furthermore, this new B/P ligand allowed the nickel-catalyzed polymerization of ethylene, which suggests that Ni0 σ-hydroborane complexes act as masked NiII boryl hydride reagents.
- Nozaki, Kyoko,Seidel, Falk William
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supporting information
(2021/12/23)
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- Quinoline diamine-containing fourth subgroup metal complex and application thereof
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The invention relates to the technical field of olefin polymerization catalysts, and particularly discloses a quinoline diamine-containing fourth subgroup metal complex and application thereof. The quinoline diamine-containing fourth subgroup metal complex has the following structure: the quinoline diamine-containing fourth subgroup metal complex provided by the invention can catalyze ethylene homopolymerisation with high activity to obtain polyethylene with high molecular weight, and catalyze ethylene and [alpha]-olefin with high activity to copolymerize to generate a copolymer with medium to high molecular weight and insertion amount; and therefore, the problem that an existing olefin polymerization catalyst cannot generate a high-molecular-weight polymer while improving the catalytic activity is solved, and the olefin polymerization catalyst has a wide application prospect.
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Paragraph 0045-0047
(2021/04/07)
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- Rh-Catalyzed Formal [3+2] Cyclization for the Synthesis of 5-Aryl-2-(quinolin-2-yl)oxazoles and Its Applications in Metal Ions Probes
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A facile and efficient strategy for the synthesis of 5-aryl-2-(quinolin-2-yl)oxazoles via rhodium-catalyzed formal [3+2] cyclization of 4-aryl-1-tosyl-1H-1,2,3-triazoles with quinoline-2-carbaldehydes has been described. The protocol employs mild conditions and offers good yields of diverse 2,5-aryloxazole derivatives with a broad reaction scope. It is amenable to gram-scale synthesis and easily transformation. Moreover, this 5-aryl-2-(quinolin-2-yl)oxazole skeleton is indeed a new fluorophore and its applications in metal ions probes are also investigated and showed fluorescent responses to mercury ion.
- Zhou, Tongtong,He, Xinwei,Zuo, Youpeng,Wu, Yuhao,Hu, Wangcheng,Zhang, Shiwen,Duan, Jiahui,Shang, Yongjia
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p. 621 - 626
(2021/02/12)
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- Preparation method and application of thioimino quinoline metal compound
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The invention relates to a preparation method of a thioimino quinoline chromium metal compound and application of the thioimino quinoline chromium metal compound in olefin polymerization. According to the invention, a quinoline skeleton is introduced, a novel metal compound of thioimino quinoline chromium is designed and synthesized, and the space effect and the electronic effect of the metal catalyst with the structure can be conveniently regulated and controlled by changing the substituent group of the ligand, so that different catalytic properties are realized. The novel metal compound of thioimino quinoline chromium reported by the invention has the characteristics of cheap and easily available raw materials, simple synthetic route and high product yield, and in the presence of MAO, all chromium complexes show medium to high activity to ethylene polymerization, and the activity is up to 9.17 * 10 g.mol (Cr). h. Therefore, the novel metal compound of thioimino quinoline chromium reported by the invention has original innovation, and can enhance the competitive power of the polyolefin high polymer material technology market in China.
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Paragraph 0017-0018
(2021/11/21)
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- Consecutive Intermolecular Reductive Amination/Asymmetric Hydrogenation: Facile Access to Sterically Tunable Chiral Vicinal Diamines and N-Heterocyclic Carbenes
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A highly enantioselective iridium- or ruthenium-catalyzed intermolecular reductive amination/asymmetric hydrogenation relay with 2-quinoline aldehydes and aromatic amines has been developed. A broad range of sterically tunable chiral N,N′-diaryl vicinal diamines were obtained in high yields (up to 95 %) with excellent enantioselectivity (up to >99 % ee). The resulting chiral diamines could be readily transformed into sterically hindered chiral N-heterocyclic carbene (NHC) precursors, which are otherwise difficult to access. The usefulness of this synthetic approach was further demonstrated by the successful application of one of the chiral vicinal diamines and chiral NHC ligands in a transition-metal-catalyzed asymmetric Suzuki–Miyaura cross-coupling reaction and asymmetric ring-opening cross-metathesis, respectively.
- Chen, Ya,Pan, Yixiao,He, Yan-Mei,Fan, Qing-Hua
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supporting information
p. 16831 - 16834
(2019/11/13)
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- Copper-catalyzed three-component reaction of: N-heteroaryl aldehydes, nitriles, and water
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An efficient and straightforward method for the synthesis of N-heteroaroyl imides has been successfully developed involving a copper-catalyzed radical-triggered three-component reaction of N-heteroaryl aldehydes, nitriles, and water. Mechanistic studies indicate that the reaction may undergo a radical-triggered Ritter-type reaction in which water serves as the oxygen source for the formation of the C-O bond. The reaction has advantages such as a broad substrate scope for the N-heteroaryl aldehydes, atom economy, and simple operation.
- Bao, Hanyang,Zhou, Bingwei,Jin, Hongwei,Liu, Yunkui
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p. 5021 - 5028
(2019/06/03)
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- Multiple dynamics of hydrazone based compounds
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Hydrazone derivatives of 2-quinolinecarboxaldehyde and 6-bromo-2-pyridinecarboxaldehyde were synthesized by sequence reactions with hydrazine derivatives. These compounds exhibited E/Z isomerization upon irradiation using a mercury lamp (250 W). The configurational changes were monitored by 1H nuclear magnetic resonance (NMR), UV-Vis and fluorescence spectroscopy. Data of concentration of the E/Z isomers versus time showed first order kinetics with constants ranging from 0.024 to 0.0799 min-1. The Z isomers were isolated by chromatographic methods and characterized by 1H NMR, UV-Vis and fluorescence spectroscopy and X-ray diffraction. The Z compounds are stable even in solution for several months. Such stability is due to a thermodynamic stabilization by the formation of an intramolecular hydrogen bond in the Z structure, which is not seen in the E configuration. Furthermore, some of the compounds were used as ligands for various metal centers (Zn2+, Co2+ and Hg2+) and their electronic properties were studied including measurements of cyclic voltammetry. The compounds studied herein allow their use as dynamic systems in dynamic combinatorial chemistry as their properties can be modulated by light, heat and the presence of metal centers. Besides, obtaining a metastable state (Z-isomer) allows the use of these compounds as photo-brakes, and therefore they can be implemented as molecular machines.
- Romero, Elkin L.,D'Vries, Richard F.,Zuluaga, Fabio,Chaur, Manuel N.
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p. 1265 - 1273
(2015/06/16)
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- NEW COMPOUNDS
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There is provided compounds of formula I,wherein R1 R2, X, R3, X1, X2, Xa, Xb, Xc, Xd, Xf, X9 and R4 have meanings given in the description (and which compounds are optionally substituted as indicated in the description), and pharmaceutically-acceptable esters, amides, solvates or salts thereof, which compounds are useful in the treatment of diseases in which inhibition of a protein or lipid kinase (e.g. a PIM family kinase, such as PIM-1, PIM-2 and/or PIM-3) is desired and/or required, and particularly in the treatment of cancer or a proliferative disease. There is also provided combinations comprising the compounds of formula I.
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Page/Page column 97
(2013/03/26)
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- Ligand design for site-selective installation of Pd and Pt centers to generate homo- and heteropolymetallic motifs
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The modular synthesis of a series of nitrogen-rich polydentate ligands that feature a common pincer-type framework is reported. These ligands allow for site-selective installation of palladium and platinum to give rise to bi- and trimetallic complexes that have d8-d8 interactions.
- Suess, Daniel L. M.,Peters, Jonas C.
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supporting information; experimental part
p. 6554 - 6556
(2010/10/21)
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- The deprotonative metalation of [1,2,3]triazolo[1,5-a]quinoline. Synthesis of 8-haloquinolin-2-carboxaldehydes
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New highly functionalized triazoloquinolines were synthesized by applying polar organometallic methods. Double metalation and functionalization provided 3,9-dihalogenated triazoloquinolines. Ring opening of the triazole with loss of nitrogen has been perf
- Ballesteros-Garrido, Rafael,Leroux, Frédéric R.,Ballesteros, Rafael,Abarca, Belén,Colobert, Fran?oise
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experimental part
p. 4410 - 4417
(2009/10/02)
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