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321.
322.
N.V. Loginova T.V. Kovalchuk R.A. Zheldakova A.A. Chernyavskaya N.P. Osipovich G.K. Glushonok G.I. Polozov V.N. Povalishev V.L. Sorokin O.I. Shadyro 《Polyhedron》2006,25(18):3603-3610
Cu (II) complexes with 3,5-di(tert-butyl)-1,2-benzenediol (I), 4,6-di(tert-butyl)-1,2,3-benzentriol (II) and sulfur-containing sterically hindered o-diphenol derivatives such as 4,6-di(tert-butyl)-3-(2-hydroxyethylsulfanyl)-1,2-benzenediol (III) and 2-[4,6-di(tert-butyl)-2,3-dihydroxyphenylsulfanyl]acetic acid (IV) have been synthesized and characterized by means of elemental analysis, TG/DTA, FT-IR, ESR, XPS, XPD and conductivity measurements. Antifungal activities of these ligands and their respective Cu (II) complexes have been determined against Aspergillus niger, Fusarium sp., Penicillium lividum, Mucor sp. and Botrytis cinerea. Most of the compounds (both the free ligands and the complexes) exert pronounced antifungal activities (RI 70%), and virtually all of them (apart from the Cu(LII)2 complex) have the highest inhibitory properties (RI = 100%) against B. cinerea. 相似文献
323.
Gabelica V Galic N Rosu F Houssier C De Pauw E 《Journal of mass spectrometry : JMS》2003,38(5):491-501
A method for determining the equilibrium association constant of a complexation reaction A + B left harpoon over right harpoon AB by electrospray ionization mass spectrometry is described. The method consists in measuring the relative intensities of the peaks corresponding to A and to AB in equimolar A-B solutions at different concentrations C(0). The results are fitted by a non-linear least-squares procedure, with the two variable parameters being the equilibrium association constant K(a) and a factor R, defined by I(AB)/I(A) = R x [AB]/[A]. The factor R is the ratio between the response factors of AB and A, and corrects for the relative electrospray responses of the complex and the free substrate A, mass discrimination of instrumental origin and/or moderate in-source dissociation. The method is illustrated with the following two systems: complexes between a double-stranded 12-base pair oligonucleotide and minor groove binders, and cyclodextrin complexes with alpha,omega-dicarboxylic acids. For the oligonucleotide complexes, it is found that the response of the complex is not dramatically different to the response of the free oligonucleotide duplex, as the double helix conformation is disturbed by the drug only to a minor extent. In the case of cyclodextrin complexes, these complexes were found to have a much higher response than free cyclodextrin. This may be due to the fact that cyclodextrin is neutral in solution, whereas the complex is charged, but it can also stem from the fact that a significant proportion of the complex is in a non-inclusion geometry. The present method requires the exact determination of the concentrations of the reactants and is applicable to 1 : 1 complexes. 相似文献
324.
Christopher T Burns 《Journal of organometallic chemistry》2003,683(1):240-248
The reaction of (hexyl)HC(mim)2 (1, mim=N-methyl-imidazol-2-yl) with (cod)PdMeCl in C6H6 yields {(hexyl)HC(mim)2}Pd(Me)Cl (3). The photochemical reaction of 3 with CH2Cl2 at 23 °C in ambient room light yields {(hexyl)HC(mim)2}Pd(CHCl2)Cl (4). It is proposed that this reaction proceeds by homolytic scission of the PdMe bond of 3. 相似文献
325.
Roland Wilberger Holger Piotrowski Marcus Warchhold Ingo‐Peter Lorenz 《无机化学与普通化学杂志》2003,629(14):2485-2492
Novel Neutral and Cationic Mono‐Aziridine Complexes of the Type [CpMn(CO)2Az], [CpCr(NO)2Az]+, and [(Ph3P)(CO)4ReAz]+ via CO‐, Hydride‐, and Chloride‐Elimination Reactions The monoaziridine complexes 1 — 5 are obtained by three differently induced substitution reactions. The photolytically induced CO substitution reaction of [CpMn(CO)3] with 2, 2‐dimethylaziridine leads to the neutral N‐coordinate aziridine complex [Cp(CO)2Mn{$\overline{N(H)CMe2C}$ H2}] ( 1 ). The protonation of [(Ph3P)(CO)4ReH] with CF3SO3H and consecutive treatment with 2, 2‐dimethylaziridine or 2‐ethylaziridine gives the salt‐like aziridine complexes [(Ph3P)(CO)4Re{$\overline{N(H)CMe2C}$ H2}](CF3SO3) ( 2 ) or [(Ph3P)(CO)4Re{ H2}](CF3SO3) ( 3 ) by hydride elimination reactions. The like‐wise salt‐like complexes [Cp(NO)2Cr{$\overline{N(H)CMe2C}$ H2}](BF4) ( 4 ) and [Cp(NO)2Cr{ H2}](CF3SO3) ( 5 ) are synthesized from [CpCr(NO)2Cl] by chloride elimination with AgX (X = BF4, CF3SO3) in the presence of 2, 2‐dimethylaziridine or 2‐ethylaziridine, respectively. As a result of X‐ray structure analyses, the metal atoms are trigonal pyramidally ( 1, 4, 5 ) or octahedrally ( 2, 3 , cis‐position) configurated; the intact three‐membered rings coordinate through the distorted tetrahedrally configurated N atoms. All compounds 1‐5 are stable with respect to the directed thermal alkene elimination to give the corresponding nitrene complexes; the IR, 1H‐ and 13C{1H}‐NMR, and MS spectra are reported and discussed. 相似文献
326.
Poverenov E Gandelman M Shimon LJ Rozenberg H Ben-David Y Milstein D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4673-4684
Novel anionic dialkyl, diaryl, and dihydride platinum(II) complexes based on the new "long-arm" hemilabile PCN-type ligand C6H4[CH2P(tBu)2](CH2)2N(CH3)2 with the general formula Li+[Pt(PCN)(R)2]- (R=Me (4), Ph (6) and H (9)) were prepared by reaction of [Pt(PCN)(R)] complexes (obtained from the corresponding chlorides) with an equivalent of RLi, as a result of the opening of the chelate ring. Alkylating agents based on other metals produce less stable products. These anionic d8 complexes are thermally stable although they bear no stabilizing pi acceptors. They were characterized by 1H, 31P[1H], 13C, and 7Li NMR spectroscopy; complex 9 was also characterized by single crystal X-ray crystallography, showing that the Li+ ion is coordinated to the nitrogen atom of the open amine arm and to the hydride ligand (trans to the P atom) of a neighboring molecule (H--Li=2.15 A), resulting in a dimeric structure. Complexes 4 and 9 exhibit high nucleophilic reactivity, upon which the pincer complex is regenerated. Reaction of 4 with water, methyl iodide, and iodobenzene resulted in the neutral complex [Pt(PCN)(CH3)] (3) and methane, ethane, or toluene, respectively. Labeling studies indicate that the reaction proceeds by direct electrophilic attack on the metal center, rather than attack on the alkyl ligand. The anionic dihydride complex 9 reacted with water and methyl iodide to yield [Pt(PCN)(H)] (8) and H2 or methane, respectively. 相似文献
327.
M. Iwan R. Łyszczek A. Ostasz Z. Rzączyńska 《Journal of Thermal Analysis and Calorimetry》2007,88(1):157-162
Properties of lanthanide 1,2,4-benzenetricarboxylates and lanthanide
1,2,4,5-benzenetetracarboxylates obtained by a classical synthesis method
and under hydrothermal conditions were compared. Solid 1,2,4-benzenetricarboxylates
and 1,2,4,5-benzenetetracarboxylates of cerium, neodymium and erbium were
prepared by a classical precipitation method. The same lanthanide compounds
were obtained also from hydrothermal reaction. All obtained products were
examined by elemental analysis. General formulae of complexes were: Ln(1,2,4-btc)·xH2O and Ln4(1,2,4,5-btec)3·yH2O. The thermal analysis
shows that hydrothermal conditions cause the coordination of less number of
water molecules to complex molecule. Because lanthanide ions exhibit the most
often the coordination number equal 8 or 9 one can conclude that the coordination
ability of carboxylic groups under hydrothermal conditions is different from
that under mild ones. Probably, in hydrothermal conditions the carboxylic
groups of 1,2,4-benzenetricarboxylate ions are able to form more coordination
bonds with lanthanide ions than under normal pressure. 相似文献
328.
《Electroanalysis》2006,18(8):814-822
Holm oak (Quercus ilex) is the dominant tree growing on serpentine soils of northeast Portugal, characterized by elevated soil concentrations of Ni and Mg, combined with low Ca concentrations. Apparently Q. ilex does not suffer from excessive concentrations of Ni in the soil. In this work we report a complexation study of nickel by the relevant ligands present in xylem sap: histidine, aspartic acid, oxalic and citric acids, at 0.10 M ionic strength and pH 5.5. Single and mixed complexes were characterized. To validate the proposed complexation model, diluted solutions of Q. ilex xylem sap were titrated with nickel. All studies were done using square‐wave voltammetry (SWV) at a hanging mercury drop electrode. Due to the dynamic nature of SWV, it is possible to obtain the conditional stability constants of the complexes formed but also to have knowledge on the kinetics of the interconversion of the species present. 相似文献
329.
Hydrotris(3, 5‐dimethylpyrazol‐1‐yl)borate and hydrotris(3‐phenylpyrazol‐1‐yl)borate decompose during reactions with [ReOCl3(PPh3)2] and [NEt4]2[Re(CO)3Br3], respectively. The generated pyrazole ligands form complexes with the rhenium(V) oxo and the rhenium(I ) tricarbonyl cores. X‐ray crystal structures of the oxo‐bridged dimer [Cl(PPh3)(O)Re(μ‐O)(μ‐Me2pz)2Re(O)(HMe2pz)Cl] ( 1 ) and [Re(CO)3(HPhpz)2(Phpz)] ( 2 ) (HMe2pz = 3, 5‐dimethylpyrazole, HPhpz = 3‐phenylpyrazole) show that the substituted pyrazoles can readily deprotonate and act as monodentate or bridging anionic ligands. Re‐N bond lengths between 2.09 and 2.14Å have been observed for the bridging and between 2.12 and 2.23Å for the terminal pyrazole ligands. 相似文献
330.
Rammile Ettelaie Brent S. Murray Emma L. James 《Colloids and surfaces. B, Biointerfaces》2003,31(1-4):195-206
To a first approximation, the primary structure of many food proteins maybe thought of as a sequence of short hydrophobic and hydrophilic blocks. The influence of this type of structure on the steric-stabilising properties of such proteins has been considered here. In line with previous studies, using Self-Consistent-Field calculations, it has been shown that the presence of such protein molecules can lead to attraction and consequently bridging flocculation of colloidal particles. In the low adsorption energy limit for the hydrophobic groups (−1kBT), it is found that the steric potential is significantly influenced by the changes in the number of adsorbed segments, as two surfaces are brought together. This is in contrast to the well-known results in the literature for the high adsorption limiting cases, where the number of such segments remains constant. In particular, the changes in the number of adsorbed hydrophobic units are observed not to be a monotonic function of the separation distance, but increase or decrease in reasonable accord with the oscillatory nature of the steric interactions, observed for various block sizes. Effects of the addition of a moderately sized hydrophilic side chain to the above molecules have also been studied. It is found that, in principle, such a modification can lead to a purely repulsive steric potential in solutions of these hybrid biopolymers. At the hydrophilic side chain sizes considered here, the surface affinity of the molecules is observed not to be drastically different compared to those of unmodified proteins. 相似文献