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101.
Compounds of general formulatrans-ArNi(PR3)2OAr' (R = Et, cyclohexyl; Ar = 2-MeC6H4, 2-FC6H4; Ar' = 4-FC6H4, 4-NO2C6H4) were synthesized by the reaction of Ar'OK with cationic nickel complexes generated by treatment of ArNi(PR3)2Cl with TlBF4. Syntheses of 4-fluorophenoxide complexes, ArNi(PR3)2OC6H4F-4, additionally give some quantities oftrans-[ArNi(PR3)2OC6H4F-4][HOC6H4F-4] adducts. Exchange reactions MeC6H4Ni(PEt3)2OC6H4F-4 + XC6H4OH 2-MeC6H4Ni(PEt3)2OC6H4X + 4-FC6H4OH were studied in THF. The equilibrium is shifted to the right as the acidity of ArOH increases. A linear relationship between lgK
eq and pK
a of XC6H4OH in DMSO was found. A conclusion concerning the strong polarization of the Ni-O bond was made on the basis of an analysis of the chemical shifts of fluorine atoms in 2-MeC6H4Ni(PEt3)2OC6H4F-4.Translated fromIvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2271, November, 1995. 相似文献
102.
1 INTRODUCTION Recently, the low-spin square-planar nickel(II) complexes and high-spin octahedral nickel(II) complexes with Schiff base ligands have received much attention in optical materials[1~3]. Some nic- kel(II) complexes are widely used as lubricating oil, rubber industry additives, a fire-resistant additive and fungicide for leather[4~7]. Also, their adducts with nitrogen have attracted broad attention due to their potential applications as organic conductors and magnetic mate… 相似文献
103.
Meyer F Demeshko S Leibeling G Kersting B Kaifer E Pritzkow H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1518-1526
Pyrazolate-based dinucleating ligands with thioether-containing chelate arms have been used for the synthesis of a family of novel tetranuclear nickel(II) complexes [L2Ni4(N3)3(O2CR)](ClO4)2 that incorporate three azido bridges and one carboxylate (R = Me, Ph). Molecular structures have been elucidated by X-ray crystallography in four cases, revealing Ni4 cores with a unique topology in which two of the azido ligands adopt an unusual mu3-1,1,3 bridging mode. The compounds were further characterized by mass spectrometry, IR spectroscopy, and variable-temperature magnetic susceptibility measurements. Magnetic data analyses indicate a combination of significant intramolecular ferromagnetic and antiferromagnetic exchange interactions that give rise to an overall S(T) = 0 ground state. The sign and the magnitude of the individual couplings have been rationalized in the framework of the common magnetostructural correlations for end-to-end and end-on azido linkages, suggesting that these correlations also remain valid for the respective fragments of multiply bridging mu3-1,1,3 azido ligands. 相似文献
104.
The kinetics of oxidation of ascorbic acid in the presence of cobalt octa-4,5-carboxyphthalocyanine sodium salt (Teraphthal) was studied. A kinetic equation was obtained and a scheme of the process was proposed. According to the scheme, the first stage is the formation of a complex of the catalyst with dioxygen, and the limiting stage is the reaction of dioxygen with the ascorbate monoanion. The influence of the pH of the medium and the presence of a transport protein (albumin) on the state and catalytic activity of Teraphthal was studied. The involvement of hydrogen peroxide and oxygen-centered radicals in the catalytic oxidation of ascorbic acid was proved. 相似文献
105.
In this B3 LYP model study, homoleptic nickel(0) ethyne complexes have been predicted as the catalyst resting state for the title reaction. Ethyne ligand coupling of Ni(C(2)H(2))(3) yields monoethyne nickelacyclopentadiene in the rate-determining step. Ethyne coordination is followed by insertion of an ethyne ligand into the Ni--C sigma bond. A highly strained monoethyne trans-nickelacycloheptatriene is formed. This trans intermediate is unable to reductively eliminate benzene without prior isomerization to a cis-structure. Instead, it rapidly collapses to a nickelacyclononatetraene. Ethyne coordination induces reductive elimination to the cyclooctatetraene complex Ni(eta(2)-C(2)H(2))(eta(2)-C(8)H(8)), followed by facile ligand exchange. Other ethyne coupling pathways have been computed to be less favored. The cyclooctatetraene ligand binds significantly weaker to nickel(0) than ethyne, both for mononuclear, and for dinuclear species. For this reason, C--C bond formation steps at Ni(2)(micro-cot) fragments have been predicted to feature prohibitively high overall reaction barriers. 相似文献
106.
A novel mixed-ligand nickel complex, [Ni(PMBP—PNH) (Py)3], [PMBP—PNH=N-(1-phenyl-3-methyl-4-benzylidene-5-pyrazolone) p-nitrobezoylhydrazide; Py = pyridine], has been synthesized by the hydrothermal method and characterized by elemental analysis, IR spectrum, thermal analysis, and single-crystal X-ray diffraction. The X-ray diffraction reveals that the nickel (II) ion in the title complex is in a slightly distorted octahedral arrangement of the ONO donor atoms of primary ligand PMBP-PNH and three N-donor atoms in the secondary ligand pyridine. 相似文献
107.
Coordinative Anchoring of Nickel Complexes on Hectorite-Layer Silicates through long-chain Diphenylphosphine Groups The treatment of sodium and calcium hectorites with 2-diphenylphosphinoethyltriethoxysilane leads, by condensation of free hydroxyl groups, to functionalized layer silicates with long-chain diphenylphosphine groups onto which nickel chloride can be coordinated. In these modified hectorites the fourth coordination site of the tetrahedrally coordinated nickel is occupied by a labile solvent molecule. On the other hand, the complex bis(2-diphenylphosphinoethyltriethoxysilane)nickel(II) chloride prepared beforehand also reacts with sodium hectorite under condensation; but the square-planar coordination of the four stable ligands (two chloride and two phosphor atoms) is maintained. This finds its expression in a significant activity decrease in catalytic reactions as compared to the aforementioned products. 相似文献
108.
实验研究结果表明双核金属酞菁类化合物MPc-PcM(M=V、Cr、Mn、Fe、Co、Ni、Cu)是催化H_2S液相氧化反应的良好催化剂,且其催化活性顺序为Co>Ni>V>Fe>Cu>Cr>Mn.采用量子化学理论计算方法(INDO/S)分析了其前线分子轨道的构成特征,结果表明这几种MPc-PcM的LUMO轨道皆为有金属离子参与形成的π轨道,但HOMO轨道间的差异却很大.M=Co、Ni、Cu、Cr时,其HOMO为π轨道;而M=Fe、Mn时,其HOMO却为σ轨道.正是在前线分子轨道的轨道类型、共轭程度及金属轨道贡献三方面因素的协同作用下,才导致MPc-PcM的催化活性顺序并非按中心金属离子价电子层d电子数的递变而呈现出规律性的变化. 相似文献
109.
Riccò M Shiroka T Carretta S Bolzoni F Femoni C Iapalucci MC Longoni G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2856-2861
The magnetic behaviour of the even-electron [Ni16Pd16(CO)40]4- cluster, in its [NnBu4]+ salt, has been investigated by magnetometry and muon spin rotation/relaxation (muSR) spectroscopy. The susceptibility measurements show an exceptionally high magnetic moment corresponding to a total spin value J=2. This suggests a Hund filling of a quadruplet ground state, quite unique in carbonyl-metal clusters. SQUID magnetometry shows a departure from the Curie-Weiss law, for T>150 K, and strong deviation from a Brillouin behaviour of the magnetisation curves. muSR spectroscopy in zero applied field shows a temperature independent decay of the muon spin polarisation, similar to that of a purely paramagnetic system. The observed muon spin repolarisation in a moderate external longitudinal field, however, invalidates this simple picture and suggests the presence of a local anisotropy field acting on the cluster's magnetic moment. A consistent interpretation of magnetometry and muSR results implies the occurrence of an additional interaction of the cluster spin with an effective crystalline field. The inclusion of this interaction in a model Hamiltonian allows us to successfully reproduce both the susceptibility and magnetisation data. 相似文献
110.
薛光荣 《分析测试技术与仪器》2004,10(3):176-179
运用了N2O—C2H2火焰原子吸收光谱法进行羰基镍粉钼含量的测定。介绍了钼最佳测定条件及呈良好线性范围的浓度,同时对样品消化处理条件及在测定中样品的干扰因素进行了综合考虑.该方法的相对标准偏差均小于1.0%(n=6),回收率均在97.0%~102.0%(n=6)之间.达到了实验室分析质量控制的要求. 相似文献