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891.
Vukadin M. Leovac Goran A. Bogdanović Valerija I. Češljević Ljiljana S. Jovanović Sladjana B. Novaković Ljiljana S. Vojinović-Ješić 《Structural chemistry》2007,18(1):113-119
The ligand, salicylaldehyde Girard-T hydrazonium chloride, [H2SalGT]Cl (1), and two complexes [Cu(HSalGT)X2]·H2O (X = Br(2); Cl(3)) were synthesized and their crystal structures were determined by single-crystal X-ray analysis. In the two isostructural
complexes, the Cu(II) is located in a square-pyramidal environment, with the chelating ligand and one halogen atom in the
basal plane and the second halogen in the apical position. The most apparent structural difference between the 1 and its complexes 2 and 3 is the orientation of the N(CH3)3 group: in 1, it is practically coplanar to the rest of the molecule, while in 2 and 3 it is oriented to the side of the axially bonded halogen, which can be explained by the C–H…X intramolecular interactions.
The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and electronic absorption
spectra. 相似文献
892.
A binuclear complex [Cu2(DTB)(DMF)4(H2O)]·2DMF (DTB = 1,4-dinitro-2,3,5,6-tetracarboxylatobenzenic anion; DMF = N,N-dimethylformamide) has been synthesized and its crystal structure determined by X-ray crystallography. In the complex Cu ion is located in a distorted square pyramidal environment with two oxygen atoms O(1) and O(3) from two carboxylate groups, another two oxygen atoms O(7) and O(8) from terminal ligands of two DMF molecules, and a fifth coordinated oxygen atom O(9) from the terminal ligand of one H2O molecule, in which the O(8) atom is situated in the apex of the pyramid. DTB as bridging ligand coordinates two Cu ions through its four carboxylate groups. The variable-temperature magnetic susceptibility of the complex was measured in the 5–300 K range. The magnetic coupling parameter is consistent with a ferromagnetic exchange between the two copper(II) centers and the data fit a binuclear magnetic exchange model based on the Hamiltonian operator ( = -2J12, 1 = 2= 1/2), giving the ferromagnetic coupling parameter of 2J = 1.80 cm- 1. This is the first example of a tetracarboxylatobenzenic bridging complex exhibiting ferromagnetic interaction. 相似文献
893.
A diastereoselective [4+2] annulation of vinyl carbodiimides with chiral N-alkyl imines has been developed to access the stereochemically rich tricyclic core of the batzelladine alkaloids. Its application to the asymmetric synthesis of batzelladine D permitted the use of long-range, directed hydrogenation and stereoselective intramolecular iodoamination as additional key steps to establish the remaining stereocenters within the natural product with excellent stereocontrol. 相似文献
894.
The MnIV complex of tetra-deprotonated 1,8-bis(2-hydroxybenzamide)-3,6-diazaoctane (MnIVL) engrossed in phenolate-amido-amine coordination is reduced by HSO3− and SO32− in the pH range 3.15–7.3 displaying biphasic kinetics, the MnIIIL− being the reactive intermediate. The MnIIIL− species has been characterized by u.v.–vis. spectra {λ max, (ε, dm3 mol−1 cm−1): 285(15 570), 330 sh (7570), 469(6472), 520 sh (5665), pH=5.42}. SO42− was the major oxidation product of SIV; dithionate is also formed (18 ± 2% of [MnIV]T) which suggests that dimerisation of SO3−• is competitive with its fast oxidation by MnIV/III. The rates and activation parameters for MnIVL + HSO3− (SO32−) → MnIIIL−; MnIIIL− + HSO3− (SO32−) → MnIIL2− are reported at 28.5–45.0 °C (I=0.3 mol dm−3, 10% (v/v) MeOH + H2O). Reduction by SO32− is ca. eight times faster than by HSO3− both for MnIVL and MnIIIL−. There was no evidence of HSO3−/SO32− coordination to the Mn centre indicating an outer sphere (ET) mechanism which is further supported by an isokinetic relationship. The self exchange rate constant (k22) for the redox couple, MnIIIL−/MnIVL (1.5 × 106 dm3 mol−1 s−1 at 25 °C) is reported. 相似文献
895.
Aarnts MP Wilms MP Peelen K Fraanje J Goubitz K Hartl F Stufkens DJ Baerends EJ Vlcek A 《Inorganic chemistry》1996,35(19):5468-5477
Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) was synthesized and characterized by UV-vis, IR, (1)H NMR, (13)C NMR, (119)Sn NMR, and mass (FAB(+)) spectroscopies and by single-crystal X-ray diffraction, which proved the presence of a nearly linear Sn-Ru-Sn unit. Crystals of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB).3.5C(6)H(6) form in the triclinic space group P&onemacr; in a unit cell of dimensions a = 11.662(6) ?, b = 13.902(3) ?, c = 19.643(2) ?, alpha = 71.24(2) degrees, beta = 86.91(4) degrees, gamma = 77.89(3) degrees, and V = 2946(3) ?(3). One-electron reduction of Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) produces the stable radical-anion [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)](*-) that was characterized by IR, and UV-vis spectroelectrochemistry. Its EPR spectrum shows a signal at g = 1.9960 with well resolved Sn, Ru, and iPr-DAB (H, N) hyperfine couplings. DFT-MO calculations on the model compound Ru(SnH(3))(2)(CO)(2)(H-DAB) reveal that the HOMO is mainly of sigma(Sn-Ru-Sn) character mixed strongly with the lowest pi orbital of the H-DAB ligand. The LUMO (SOMO in the reduced complex) should be viewed as predominantly pi(H-DAB) with an admixture of the sigma(Sn-Ru-Sn) orbital. Accordingly, the lowest-energy absorption band of the neutral species will mainly belong to the sigma(Sn-Ru-Sn)-->pi(iPr-DAB) charge transfer transition. The intrinsic strength of the Ru-Sn bond and the delocalized character of the three-center four-electron Sn-Ru-Sn sigma-bond account for the inherent stability of the radical anion. 相似文献
896.
Antolín R Borge G Posada T Raposo JC Seara I Etxebarria N 《Journal of AOAC International》2004,87(5):1218-1223
A validation study was carried out in order to evaluate the efficiency of inductively coupled plasma-optical emission spectrometry (ICP-OES) for the analysis of minor elements (manganese, chromium, copper, iron, and titanium) in aluminium alloys. Aluminium casting samples were obtained by adding compressed powder compacts of each alloying element and aluminium (minitablets) to aluminum baths in a laboratory crucible furnace. Digestion of solid samples was performed using concentrated HCI and H202 35% (v/v) previous to analysis by ICP-OES without any matrix separation. This solution-based method was validated considering direct current arc spectrometry as the reference method based on direct analysis without any pretreatment of the solid samples considered. Univariate statistical procedures were carried out, for which precision <3% and trueness of the analytical results were taken into account. 相似文献
897.
Jocelyn M. Bouzaid R. L. Frost W. N. Martens 《Journal of Thermal Analysis and Calorimetry》2007,89(2):511-519
The thermal stability and thermal decomposition pathways for synthesized composite iowaite/woodallite have been determined
using thermogravimetry analysis in conjunction with evolved gas mass spectrometry. Dehydration of the hydrotalcites occurred
over a range of 56–70°C. The first dehydroxylation step occurred at around 255°C and, with the substitution of more iron(III)
for chromium(III) this temperature increased to an upper limit of 312°C. This trend was observed throughout all decomposition
steps. The release of carbonate ions as carbon dioxide gas initialised at just above 300°C and was always accompanied by loss
of hydroxyl units as water molecules. The initial loss of the anion in this case the chloride ion was consistently observed
to occur at about 450°C with final traces evolved at 535 to 780°C depending of the Fe:Cr ratio and was detected as HCl (m/z=36). Thus for this to occur, hydroxyl units must have been retained in the structure at temperatures upwards of 750°C. Experimentally
it was found difficult to keep CO2 from reacting with the compounds and in this way the synthesized iowaite-woodallite series somewhat resembled the natural
minerals. 相似文献
898.
899.
J. Goworek W. Stefaniak Agnieszka Kierys Mariola Iwan 《Journal of Thermal Analysis and Calorimetry》2007,87(1):217-222
Mesoporous silica material of MCM-41 type was synthesized by co-condensation
of highly concentrated octyltriethoxysilane (OTEOS), octadecyltriethoxysilane
(ODTEOS) and tetraethoxysilane (TEOS). The obtained hybrid materials were
characterized using XRD, TG-DSC and low temperature adsorption/desorption
of nitrogen. It was shown that the applied method of synthesis allows to obtain
silica of MCM-41 type with a high degree of hydrocarbon saturation. 相似文献
900.
Nanosized copolymer latex of hydroxypropylmethylcellulose (HPMC) grafted with ethyl acrylate (EA) and dimethylaminoethyl methacrylate
(DMAEMA) has been prepared by acidifying submicron-sized latex particles synthesized by soap-free emulsion graft copolymerization
using potassium persulfate (KPS) as initiator. The effects on the diameter of the latex particles of different conditions,
for example concentration of DMAEMA, amount of HPMC, and ratio of HCl to DMAEMA for acidification, were investigated. It was
found that increasing the mole ratio of HCl to DMAEMA to 1.0 and increasing the DMAEMA content both resulted in a decrease
in particle diameter, whereas increasing the amount of HPMC resulted in larger particle sizes. Measurement by dynamic light
scattering (DLS) revealed the diameter of the latex particles was >200 nm before acidification and <100 nm after acidification.
Evidence of grafting was obtained by use of Fourier transform infrared (FTIR) spectroscopy. Transmission electron microscopy
(TEM) was used to characterize the morphology of the copolymer particles before and after acidification. 相似文献