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1.
Haixing Guan Qianwen Zhang Prof. Dr. Patrick J. Walsh Prof. Dr. Jianyou Mao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(13):5210-5215
A unique nickel/organic photoredox co-catalyzed asymmetric reductive cross-coupling between α-chloro esters and aryl iodides is developed. This cross-electrophile coupling reaction employs an organic reductant (Hantzsch ester), whereas most reductive cross-coupling reactions use stoichiometric metals. A diverse array of valuable α-aryl esters is formed under these conditions with high enantioselectivities (up to 94 %) and good yields (up to 88 %). α-Aryl esters represent an important family of nonsteroidal anti-inflammatory drugs. This novel synergistic strategy expands the scope of Ni-catalyzed reductive asymmetric cross-coupling reactions. 相似文献
2.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
3.
Fei Chang Dongheng Zhang Haijian Yang Haibin Song 《Journal of organometallic chemistry》2004,689(5):936-946
The synthesized 1-aryliminomethylenylnaphthalen-2-ol derivatives reacted with nickel chloride to form bis(1-aryliminomethylenylnaphthalen-2-oxy)nickel complexes. All resultant compounds were structurally characterized by elemental analyses, IR and H NMR, and the structures of the formed complexes were elucidated by X-ray crystal structure analysis. The complexes show high catalytic activities for the vinyl polymerization of norbornene in the presence of methylaluminoxane. The catalytic activity variations have been followed by gas chromatography through monitoring the conversion of norbornene. 相似文献
4.
J. T. Hoeft M. Polcik D. I. Sayago M. Kittel R. Terborg R. L. Toomes J. Robinson D. P. Woodruff M. Pascal G. Nisbet C. L. A. Lamont 《Surface science》2003,540(2-3):441-456
The local adsorption geometry of CO adsorbed in different states on Ni(1 0 0) and on Ni(1 0 0) precovered with atomic hydrogen has been determined by C 1s (and O 1s) scanned-energy mode photoelectron diffraction, using the photoelectron binding energy changes to characterise the different states. The results confirm previous spectroscopic assignments of local atop and bridge sites both with and without coadsorbed hydrogen. The measured Ni–C bondlengths for the Ni(1 0 0)/CO states show an increase of 0.16 ± 0.04 Å in going from atop to bridge sites, while comparison with similar results for Ni(1 1 1)/CO for threefold coordinated adsorption sites show a further lengthening of the bond by 0.05 ± 0.04 Å. These changes in the Ni–CO chemisorption bondlength with bond order (for approximately constant adsorption energy) are consistent with the standard Pauling rules. However, comparison of CO adsorbed in the atop geometry with and without coadsorbed hydrogen shows that the coadsorption increases the Ni–C bondlength by only 0.06 ± 0.04 Å, despite the decrease in adsorption energy of a factor of 2 or more. This result is also reproduced by density functional theory slab calculations. The results of both the experiments and the density functional theory calculations show that CO adsorption onto the Ni(1 0 0)/H surface is accompanied by significant structural modification; the low desorption energy may then be attributed to the energy cost of this restructuring rather than weak local bonding. 相似文献
5.
Some nickel, copper, and silver salts or complexes are efficient catalysts for the oxidation of benzylic ethers with oxygen in 1,2-dimethoxyethane. Salts of the weakly coordinating anion trifluoroacetate are particularly efficient, approaching (and, in some cases, improving) the yields obtained with cobalt(II) chloride, the best catalyst so far reported. 相似文献
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Ni + Mo + Si composite coatings were prepared by co-deposition of nickel with molybdenum and silicon powders from a nickel solution in which Mo and Si particles were suspended by stirring. The layers have been deposited on a carbon steel substrate (St3S) under galvanostatic conditions. The content of Si in deposited layers was about 2-5 wt.% depending on deposition current density and the value of electric charge. For comparison Ni + Mo composite coatings were obtained under analogous current conditions. Composite coatings of enhanced Si content (15 wt.%) were deposited from an electrolyte in which 40 g/dm3 of Si covered with electroless plated nickel was dispersed. Deposition current density was equal 0.1 A/cm2 and the value of electric charge Q = 500 C/cm2. The thickness of the coatings was about 100-300 μm depending on their kind, electric charge and the deposition current density. Surface and cross-section morphology were investigated by scanning electron microscope (SEM). All deposited coatings are characterized by great, developed surface area. No internal stresses causing their cracking were observed. Chemical composition of the layers was determined by X-ray fluorescence spectroscopy (XRF) method and quantitative X-ray analysis (QXRD). It was stated, that the content of molybdenum and silicon in Ni + Mo + Si coatings depends on deposition current density and the amount of the powder in bath. The results of structural investigation of the obtained layers by the X-ray diffraction (XRD) method show, that they consist in crystalline Mo or Mo and Si phases built into Ni matrix. Moreover, Ni + Mo + Si composite coatings were modified by thermal treatment. It has been found that the thermal treatment of Ni + Mo + Si composite coatings caused that the new phases (NiSi, Mo2Ni3Si and Ni6Mo6C1.06) were obtained. 相似文献