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51.
Bruce R. McGarvey 《Coordination chemistry reviews》1998,170(1):75-92
Using a newly proposed approach involving an internally consistent set of equations, the ligand field parameters Δ/ξ, V/ξ and k are obtained from literature values of the g matrix for strong field d5 systems of various conformations in which |Δ/ξ|≤10. Qualitative analysis of the observed results is done using the Angular Overlap Model, AOM. 相似文献
52.
O. G. Shakirova D. Yu. Naumov Yu. G. Shvedenkov N. I. Alferova G. V. Dolgushin L. G. Lavrenova 《Journal of Structural Chemistry》2003,44(4):642-649
A new trinuclear nickel(II) complex with 4-(pyridyl-2)-1,2,4-triazole (pytrz), [Ni3(pytrz)6(H2O)6](NO3)6, has been synthesized, and its crystal structure has been determined. The compound was studied by X-ray phase analysis (XRPA), magnetochemical measurements, and electronic and IR spectroscopy. 相似文献
53.
Tapan Kumar Lal John F. Richardson Mark S. Mashuta Robert M. Buchanan Rabindranath Mukherjee 《Polyhedron》1997,16(24):1248-4336
Synthesis and characterization of a nitrite-bound copper(II) compound [CuL4)2(ONO)]ClO4 have been achieved (L4 = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L4 provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the dx2−y2 orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible CuII---CuI response [cathodic peak potential, Epc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible CuII---CuI redox response [
]. 相似文献
54.
Fatma Alper 《Journal of organometallic chemistry》2006,691(12):2734-2738
Pentacarbonylpyrazinetungsten(0), (CO)5W(pyz), is not stable in solution in polar solvents such as acetone or dichloromethane and undergoes conversion to a bimetallic complex, (CO)5W(pyz)W(CO)5 plus free pyrazine. These three species exist at equilibrium. Using the quantitative 1H NMR spectroscopy, the equilibrium constant could be determined to be Keq = (5.9 ± 0.8) × 10−2 at 25 °C. Introducing a second pyrazine ligand into the molecule does not stabilize the complex, as cis-W(CO)4(pyz)2 was found to be less stable than W(CO)5(pyz) and, therefore, could not be isolated. However, introducing trimethylphosphite as a donor ligand into the complex leads to the stabilization of the carbonyl-pyrazine-metal(0) complexes, as shown by the synthesis of cis-W(CO)4[P(OCH3)3](pyz). This complex could be isolated from the reaction of the photogenerated W(CO)4[P(OCH3)3](tetrahydrofuran) with trimethylphosphite upon mixing for 2 h at 10 °C in tetrahydrofuran and characterized by elemental analysis, IR, MS, 1H, 13C, and 31P NMR spectroscopy. 相似文献
55.
V. A. D’yakonov R. K. Timerkhanov A. G. Ibragimov U. M. Dzhemilev 《Russian Chemical Bulletin》2007,56(11):2232-2235
Catalytic cycloalumination of cyclonona-1,2-diene upon treatment with Et3Al and EtAlCl2 in the presence of Cp2ZrCl2, leading to 10-ethyl-10-aluminabicyclo[7.3.01,9]dodec-8-ene (1) and 11-ethyl-11-aluminatricyclo[10.7.01,12.02,10]nonadeca-9,12-diene, respectively, was accomplished in high yields. A possibility for the selective transformation of compound
1 to 1-allyl-9-(pent-4-enyl)cyclonon-1-ene and 10-hydroxybicyclo[7.3.01,9]dodec-8-ene in one preparative step was demonstrated.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2156–2159, November, 2007. 相似文献
56.
WEI Ping-Rong JIA Lu LIU Chang-Rang FAN Yao-TingDepartment of Chemistry Zhengzhou University Zhengzhou Henan ChinaGAO SongResearch Center of Rare Earth Chemistry Peking University Beijing China 《中国化学》1994,12(6):503-508
The two complexes [Ni(oxen)Cu(L)2](ClO4)2.xH2O (L=2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen)) have been synthesized, where oxen is N,N'-bis(2-aminoethyl)oxamido di-anion. The crystal structure of [Ni(oxen)Cu(bpy)2](ClO4)2.CH3OH has been determined by X-ray diffraction method. The crystal is triclinic system, space group P1 with a=12.179(1),b=12.298(2), c=11.476(2) A, a=97.57(1), B=97.52(1), 7=80.29(2), V=1669.04(67) A3, Z=2, Dcalcd=1.667 g/cm3. The structure has been refined to final R of 0.076 and Rw of 0.080, respectively. The complexes have an extended oxamido-bridged structure and consist of Ni(Ⅱ) ion in a square planar environment and Cu(Ⅱ) ion in a distorted octahedral environment. 相似文献
57.
Xe(OTeF5)2 reacts with Sb(OTeF5)3 under the formation of [Xe2(OTeF5)3]+[Sb(OTeF5)6]-. From SO2ClF solution a yellow solvate [F5TeOXe]+·SO2ClF· [Sb(OTeF5)6]- is formed with the crystal data: a = 1028.1(1), b = 1040.9(1), c = 1780.2(3) pm, α = 98.07(1), β = 97.68(1), γ = 105.82(1)°, space group . The O-Xe···O fragment is essentially linear (176.1(2)°), and the two Xe-O distances are quite different 197.1(4) and 242.6(4) pm. 相似文献
58.
To explore the properties of cyclodextrins (CDs) as an optical sensing phase, the behavior of immobilized CD in interaction with analytes was studied in this work. CDs having different cavity sizes were immobilized onto the surface of infrared (IR) internal reflection-sensing element (IRE) to kinetically monitor the behavior of CD in interaction with analytes. Several aromatic compounds having various molecular sizes and functional groups were used to characterize the interaction mechanism. A two-layer modification method was proposed in this work, which utilized a thin hydrophobic film (polyvinyl benzyl chloride) to stick on the IRE and to covalently bond to the CDs through an ethylene diamine linker. The synthesized CD phases exhibited high stability in aqueous solution. To analyze the behavior during the formation of complexes between the guest molecules and the CD phases, we modeled the interaction behavior and treated the kinetic data with the theoretical equations developed in this work. The results indicate that the behavior of the interaction between guest molecules and CDs was explained by considering the formation of two types of complexes: adsorbed complexes and inclusion complexes. The formation of the inclusion complexes was relatively fast, the time required to reach equilibrium could be shorter than a few minutes. The adsorbed complexes were also observed, but their rate of formation was relatively slow; equilibrium could be reached at times greater than 60 min. Based on the signals observed under equilibrium conditions, the concentration of inclusion complexes was approximately three times than that of the adsorbed complexes. 相似文献
59.
Sabry K. Mohamed 《Analytica chimica acta》2006,562(2):204-209
A poly(vinyl chloride)-based membrane of 2,9-dimethyl-4,11-diphenyl-1,5,8,12-tetraazacyclotetradeca-1,4,8,11-tetraene (DDTCT) with sodium tetraphenyl borate (STB) as an anion excluder and dibutyl phthalate (DBP), dibutyl butylphosphonate (DBBP), tris(2-ethylhexyl) phosphate (TEP) and tributyl phosphate (TBP) as plasticizing solvent mediators was prepared and investigated as a Ga(III)-selective electrode. The best performance was observed with the membrane having the ligand-PVC-DBP-STB composition 1:4:1:1, which worked well over a wide concentration range (1.45 × 10−6 to 0.1 mol L−1) with a Nernstian slope of 28.7 mV per decade of activity between pH 4.0 and 10.0. This electrode showed a fast response time of 12 s and was used over a period of 100 days with good reproducibility (s = 0.3 mV). The selectivity coefficients for monovalent, divalent and trivalent cations indicate excellent selectivity for Ga(III) ions over a large number of cations. Anions such as Cl− and SO42− do not interfere and the electrode also works satisfactorily in partially water-alcohol medium. The practical utility of the membrane sensor has also been observed in solutions contaminated with detergents, i.e., cetyltrimethylammonium bromide and sodium dodecyl sulfate and used for the determination of gallium in nickel alloy, fly-ash and biological samples. 相似文献
60.
《Electroanalysis》2005,17(7):613-618
For polyelectrolyte complex between cationic surfactant and polyanion, the adsorptive voltammetry at carbon paste electrode using an electroactive cationic surfactant was examined. The adsorption state of the cationic surfactant in the complexes at CPE was estimated from the half‐height width of the oxidation waves. The half‐height width for poly(styrene sulfonate) was independent of the molecular weight, and was same as that for poly(vinyl sulfate). The half‐height width for heparin was broad and different from that of the vinyl polyanions. According to the analysis by Frumkin isotherm, the interaction between cationic surfactants was attractive in heparin complex at CPE, however, in the vinyl polyanion complexes at CPE the interaction was non‐cooperative as that predicted with the Langmuir isotherm. In spite of the same adsorption state, the concentration dependency of the peak current for poly(styrene sulfonate) was quite different from that for poly(vinyl sulfate). The concentration dependence indicated the reactive property of each polyanion on the association with the cationic surfactant in aqueous solution. 相似文献