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Kraikivskii P. B. Saraev V. V. Matveev D. A. Zelinskii S. N. Tkach V. S. 《Russian Journal of Coordination Chemistry》2003,29(6):431-434
Reactions of aluminium tribromide with the Ni(0) phosphine and phosphite complexes are studied by EPR method. AlBr3was found to cause the oxidation of the transition metal in the (PPh3)4Ni complex to the univalent state with the formation of the tetracoordinated (PPh3)3NiBr complex. With an excess of AlBr3, the phosphine ligands are eliminated from the coordination sphere of Ni(I), and the coordinatively unsaturated complexes are destroyed to give the colloidal nickel. In the reaction of (P(OEt)3)4Ni with AlBr3, Ni(0) is also oxidized to Ni(I), but the acido ligand is not eliminated even with a 15-fold excess of the Lewis acid. The activity of catalytic systems on the basis of the Ni(0) phosphine complexes and the Lewis acids in the low-molecular oligomerization reactions of olefines is determined by the cationic coordinatively unsaturated Ni(I) complexes formed in these systems. 相似文献
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B. G. Gol’denberg A. Yu. Abramskii A. G. Zelinskii A. I. Maslii E. A. Maksimovskii V. I. Kondrat’ev V. P. Korol’kov K. E. Kuper E. V. Petrova V. F. Pindyurin 《Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques》2011,5(1):159-165
The development of a low-cost technology to manufacture high-contrast X-ray LIGA masks is topical because this technology
is important for various applied research on microstructured products with minimum element sizes of 10–50 μm, such as microfluid
analytical systems, selective waveguide mesh-based elements to control terahertz (THz) radiation, microshaped optical elements
for the visible range, etc. Technological particularities of mask manufacture are considered. A method to check the quality
of masks is presented. Test microproducts manufactured using the produced deep X-ray lithography masks are demonstrated. 相似文献
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Tkach V. S. Zelinskii S. N. Ratovskii G. V. Proidakov A. G. Schmidt F. K. 《Russian Journal of Coordination Chemistry》2004,30(10):703-708
IR and NMR data showed that the ionic complex Pd2(CHCC6H5)2(C5H7O2)3(BF3)2BF4 isolated in the reaction Pd(Acac)2 + PA + 5BF3OEt2 (Acac is C5H7O2, PA is phenylacetylene) is an adduct of two complexes, namely, (Acac)PdBF4 and [(PA)2Pd(C3-Acac · BF3)]+(Acac · BF3)– (coordinatively unsaturated). On dissolution in deuteroacetone or deuteromethanol, the [(Acac)PdF2BF2Pd(C3-Acac · BF3)(PA)2]+(Acac · BF3)– adduct decomposed to Pd(Acac)2, 2BF3 · L (L = (CD3)2CO, CD3OD) and the [L(PA)2Pd(C3-Acac]+BF4
– complex. 相似文献
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Saraev V. V. Kraikivskii P. B. Zelinskii S. N. Ratovskii G. V. Tkach V. S. Shmidt F. K. 《Russian Journal of Coordination Chemistry》2001,27(11):757-762
The reactions of the individual cationic complex [(PPh3)3Ni]BF4with unsaturated hydrocarbons (ethene, propene, and styrene), as well as the reaction of the -alkyl Ni(I) complex (PPh3)2Ni–CH(COOC2H5)2(obtained in situ) with ethene, were studied using EPR, UV, and NMR spectroscopy. It was found that stable dimeric carbocationic -alkyl Ni(I) complexes are intermediates in the reactions of unsaturated hydrocarbons with cationic Ni(I) complexes. The transformations of unsaturated hydrocarbons on cationic Ni(I) complexes were explained in terms of an experimentally justified ionic coordination mechanism. A stable mononuclear Ni(I) complex with a Ni–C -bond was synthesized and characterized using EPR. An organonickel(I) complex with - and -bonded carbon atoms was identified using EPR and NMR methods. 相似文献
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Genrikh E. Zelinskii Alexander S. Belov Alexander S. Chuprin Alexander A. Pavlov Anna V. Vologzhanina Ekaterina G. Lebed 《Journal of Coordination Chemistry》2017,70(13):2313-2333
Template cross-linking of nioxime using equimolar amounts of boric and 4-vinylphenylboronic acids on an iron(II) ion as a matrix gave a mixture of mono- and divinyl-terminated clathrochelate products, which were chromatographically isolated in moderate yields and characterized by X-ray diffraction. The target complex FeNx3(BOCH3)(4-BC6H4CH=CH2) with non-equivalent capping groups was also obtained in a low yield using a transmetallation (re-boronation) of its dimethoxyboron-capped clathrochelate precursor. Re-boronation of the monomethoxyboron-capped cage complex with benzene-1,4-diboronic acid as a bifunctional Lewis-acidic agent afforded mainly the clathrochelate product of its 1:1 re-boronation having a terminal B(OH)2 group. The iron(II) clathrochelate with labile triethylantimony capping groups underwent a transmetallation on the surface of silica gel giving an immobilized Sb, Si-capped macrobicyclic intermediate. Its desorption with 4-vinylphenylboronic acid unexpectedly gave the monovinyl-terminated iron(II) semiclathrochelate as the major product, isolated in a high yield; it was X-ray structurally characterized. The geometry of FeN6-coordination polyhedra of the above semi- and clathrochelates is intermediate between a trigonal prism and a trigonal antiprism; that of the monocapped iron(II) semiclathrochelate is more TAP-distorted and its pseudoencapsulated iron(II) ion is shifted from the center of this polyhedron by 0.02 Å in the direction of the capping boron atom. 相似文献
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Genrikh E. Zelinskii Ilya P. Limarev Anna V. Vologzhanina Valentina A. Olshevskaya Anton V. Makarenkov Pavel V. Dorovatovskii Alexander S. Chuprin Mikhail A. Vershinin Semyon V. Dudkin Yan Z. Voloshin 《Molecules (Basel, Switzerland)》2021,26(12)
A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate precursor with amine N-nucleophiles of different natures in various solvents was performed. One of its two chlorine atoms with morpholine or diethylamine in dichloromethane gave reactive monohalogenoclathrochelate complexes functionalized with abiorelevant substituents. Further nucleophilic substitution of their remaining chlorine atoms with propargylamine in DMF led to morpholine- and diethylamine-functionalized monopropargylamine cage complexes, the molecules of which contain the single terminal C≡C bond. Their “click” 1,3-cycloaddition reactions in toluene with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate gave spacer-containing di- and tritopic iron(II) carboranoclatrochelates formed by a covalent linking between their different polyhedral(cage) fragments. The obtained complexes were characterized using elemental analysis, MALDI-TOF mass, UV-Vis, 1H, 1H{11B}, 11B, 11B{1H}, 19F{1H} and 13C{1H}-NMR spectra, and by a single crystal synchrotron X-ray diffraction experiment for the diethylamine-functionalized iron(II) carboranoclathrochelate. Its encapsulated iron(II) ion is situated almost in the center of the FeN6-coordination polyhedron possessing a geometry intermediate between a trigonal prism and a trigonal antiprism with a distortion angle φ of approximately 28°. Conformation of this hybrid molecule is strongly affected by its intramolecular dihydrogen bonding: a flexibility of the carborane-terminated ribbed substituent allowed the formation of numerous C–H…H–B intramolecular interactions. The H(C) atom of this carborane core also forms the intermolecular C–H…F–B interaction with an adjacent carboranoclathrochelate molecule. The N–H…N intermolecular interaction between the diethylamine group of one hybrid molecule and the heterocyclic five-membered 1H-[1,2,3]-triazolyl fragment of the second molecule of this type caused formation of H-bonded carboranoclathrochelate dimers in the X-rayed crystal. 相似文献
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By using the classical Helly theorem, one cannot obtain information about a family of convex compact sets in the n-dimensional Euclidean space if it is known that only subfamilies consisting of k elements, 0 < k n, have nonempty intersections. We modify the Helly theorem to fix this issue and investigate the behavior of generalized convex families. 相似文献