14126-37-5Relevant articles and documents
Catalysis of Cross-Coupling and Homocoupling Reactions of Aryl Halides Utilizing Ni(0), Ni(I), and Ni(II) Precursors; Ni(0) Compounds as the Probable Catalytic Species but Ni(I) Compounds as Intermediates and Products
Manzoor, Adeela,Wienefeld, Patrick,Baird, Michael C.,Budzelaar, Peter H.M.
, p. 3508 - 3519 (2017/10/03)
Both Ni(0) and Ni(I) compounds are believed to exhibit cross-coupling catalytic properties under various conditions, and the compounds Ni(PPh3)4 and NiCl(PPh3)3 are compared as catalysts for representative Suzuki-Miyaura and Heck-Mizoroki cross-coupling reactions. The Ni(0) compound exhibits catalytic activities, for cross-coupling of chloro and bromoanisole with phenylboronic acid and of bromobenzene with styrene, yielding results which are comparable with those of many palladium-based catalysts, but our findings with NiCl(PPh3)3 are at this point unclear. It seems to convert to catalytically active Ni(0) species under Suzuki-Miyaura reaction conditions and is ineffective for Heck-Mizoroki cross-coupling. The paramagnetic Ni(I) compounds NiX(PPh3)3 (X = Cl, Br, I) are characterized for the first time by 1H NMR spectroscopy and are found to exhibit broad meta and para resonances at δ 9-11 and 3-4, respectively, and very broad ortho resonances at δ 46; these resonances are very useful for detecting Ni(I) species in solution. The chemical shifts of NiCl(PPh3)3 vary with the concentration of free PPh3, with which it exchanges, and are also temperature-dependent, consistent with Curie law behavior. The compound trans-NiPhCl(PPh3)2, the product of oxidative addition of chlorobenzene to Ni(PPh3)4 and a putative intermediate in cross-coupling reactions of chlorobenzene, is found during the course of this investigation to exhibit entirely unanticipated thermal lability in solution in the absence of free PPh3. It readily decomposes to biphenyl and NiCl(PPh3)2 in a reaction relevant to the long-known but little-understood nickel-catalyzed conversion of aryl halides to biaryls. Ni(I) and biphenyl formation is initiated by PPh3 dissociation from trans-NiPhCl(PPh3)2 and formation of a dinuclear intermediate, a process which is now better defined using DFT methodologies.
LINEAR PYRIDAZINE AND PYRROLE COMPOUNDS, METHOD FOR OBTAINING THEM AND APPLICATIONS
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Page/Page column 32, (2010/02/16)
The present invention relates to linear pyridazine compounds, and more particularly to those of these compounds which are oligopyridazine compounds, to processes for obtaining them, to their uses, and also to their reduction to pyrroles and to the uses of the pyrrole, pyridazinylpyrrole and oligopyrrole compounds obtained. The invention relates in particular to the uses as medicaments, in particular for treating pathologies such as cancer, bacterial infections or parasitic infections, and also the applications in the materials, environmental, electronics and optics field.
Ethylene polymerization and oligomerization catalyzed by bulky β-diketiminato Ni(II) and β-diimine Ni(II) complexes/methylaluminoxane systems
Zhang, Junkai,Ke, Zhuofeng,Bao, Feng,Long, Jieming,Gao, Haiyang,Zhu, Fangming,Wu, Qing
, p. 31 - 39 (2008/10/09)
β-Diketiminato complexes Ni{(N(Ar)C(Me))2CH}Br (9), Ni{(N(Ar)C(Me))2CH} Pph3Br (10) and β-diimine complexes Ni{(N(Ar)C(Me))2CH2}Br2 (5) (Ar = 2,6-iPr2C6H3 (a), 2,6-Me2C6H3 (b)) were used as catalyst precursors for ethylene polymerization in the presence of methylaluminoxane (MAO). High molecular weight ethylene polymers as well as short chain oligomers (C4-C8) were simultaneously produced from the catalysis reactions. Ethylene polymers obtained by using these β-N-N Ni(II)/MAO catalyst systems are mainly methyl branched. Small amounts of even number branches were also observed in the 13C NMR spectra of the obtained ethylene polymers, which are believed generating from the incorporation of simultaneously produced α-olefins. Except methyl branch and the branches derived from the incorporation of α-olefin oligomers, the formation of other branch types via the chain walking process is not favored in β-diketiminato Ni(II) systems.
