A green and efficient oxidation of benzylic alcohols using H2O2 catalyzed by montmorillonite K-10 supported CoCl2

Primary and secondary benzylic alcohols were oxidized to the corresponding carbonyl compounds in good to high yields by environmentally friendly and green oxidant, H2O2 catalyzed by montmorillonite K-10 supported cobalt（Ⅱ） chloride.     

A green and efficient deoximation using H202 catalyzed by montmorillonite-K10 supported COC12

Oximes were oxidized to the corresponding carbonyl compounds in good to high yields by environmentally friendly and green oxidant, H202 catalyzed by montmorillonite K-10 supported cobalt（Ⅱ） chloride.     

Ni^2—交换蒙脱石中的镍物种及焙烧温度影响研究

对一组自制Ｎｉ＾２＋交换蒙脱石样品中镍物种的存在在形及焙烧温度影响进行了ＴＰＲ和ＸＲＤ考察结果表明，样品中镍负载量等于或小于Ｎｉ＾２＋的交换量时，镍主要以难还原听可交换性阳离子Ｎｉ（ＯＨ）＾ｑ＋ｘ和易还原的自由态镍Ｎｉ（ＯＨ）２或ＮｉＯ两种形式存在。     

基于蒽酰亚胺基团的新型Fe3+和Hg2+化学敏感器

含蒽酰亚胺基团的化合物N-(2-(6-氨基吡啶))-9-蒽酰亚胺(L¹)对Fe³⁺表现出灵敏的荧光增强响应.L¹的衍生物N,N-’(2,6-吡啶基)-二(9-蒽酰亚胺)(L²)对Hg²⁺在紫外-可见吸收光谱和荧光光谱上显示了良好的识别性.即使在其它金属阳离子存在下,L¹和L²分别对于Fe³⁺和Hg²⁺仍然表现出较好的选择性.     

原位反应法制备镍三乙烯四胺配合物/蒙脱土纳米复合体

将蒙脱土的硅酸盐晶层空间作为微反应场所,用微波加热先将钠基蒙脱土转化为镍基蒙脱土,再引入三乙烯四胺配体,使配体与镍离子在蒙脱土层间原位发生配位反应,制得配合物/蒙脱土纳米复合体.XRD结果表明蒙脱土的层间距在引入三乙烯四胺后明显变大.紫外可见漫反射光谱、热分析和元素分析结果表明三乙烯四胺与N i2+离子在蒙脱土层间形成了配合物.     

Development of new Cd2+ and Pb2+ Lennard-Jones parameters for liquid simulations

We present new Lennard-Jones parameters for Cd2+ and Pb2+ ion-water interactions and describe a general methodology to obtain these parameters for any ion. Our strategy is based on the adjustment of ion parameters to reproduce simultaneously experimental absolute hydration free energy and structural properties, namely, g(r) and coordination numbers, obtained from X-ray liquid scattering and quantum mechanical/molecular mechanical (QM/MM) calculations. The validation of the obtained parameters is made by the calculation of dynamical properties and comparing them with experimental values and theoretical results from the literature. The transferability of parameters is checked by the calculation of thermodynamic, structural, and dynamical properties cited above with four different water models. The results obtained for Cd2+ and Pb2+ show an overall agreement with reference values. The absolute hydration free energy calculated with the TIP3P, SPC/E, SPC, and TIP4P water models presents, respectively, percent differences of 3.8, 3.0, 4.3, and 7.2% for lead(II) and 9.8, 8.4, 10.2, and 14.1% for cadmium(II) when compared with experimental values. Ion-water mean distance and coordination numbers for the first coordination shell are in good agreement with experimental and QM/MM results for both ions. Cd2+ shows a lesser diffusion coefficient compared to that of Pb2+ despite its smaller atomic radius, indicating a more persistent first coordination shell for the cadmium(II) ion, a result confirmed with calculations of the mean residence time of water molecules in the first coordination shell.     

FT-IR spectroscopic investigations of adsorption of 2-, 3- and 4-pyridinecarboxamide on montmorillonite and saponite from Anatolia

The adsorption of 2-, 3- and 4-pyridinecarboxamide (PYCA) on montmorillonite and saponite has been investigated using FT-IR spectrometry. The intercalation of 2-, 3- or 4-pyridinecarboxamide within montmorillonite or saponite has been shown by X-ray diffraction to increase the interlayer spacings. PYCA interacted with clays by direct or indirect coordination (through water molecules) to the exchangeable cations. It is concluded that endocyclic nitrogen is mainly involved in coordination. Amido group hydrogens and oxygen, however, may involve weak H-bonding interaction with water molecules.     

One octarepeate expansion to the human prion protein alters both the Zn2+ and Cu2+ coordination environments within the octarepeate domain

The influence of a single octarepeat expansion on the Cu(II) and Zn(II) coordination environments within the octarepeat domain of the human prion protein is examined. Using X-ray absorption spectroscopy and diethyl pyrocarbonate labeling studies, we find that at low copper concentrations the "normal" octarepeat domain (four PHGGGWGQ repeats) coordinates Zn(II) in an (N/O)(6) coordination environment with two histidine residues and Cu(II) in a redox-inactive (N/O)(4) coordination environment using one imidazole residue. Expansion of the octarepeat region by one repeat (five PHGGGWGQ repeats) yields a three-histidine (N/O)(6) coordination environment for Zn(II) and a two-histidine (N/O)(4) coordination environment for Cu(II) at low copper concentrations. This Cu(II)[(N/O)(2)-histidine(2)] coordination motif is redox-active and capable of generating H(2)O(2) under reducing aerobic conditions.     

Complex Formation Products in the GeO2–Tartaric Acid–CuCl2–1,10-Phenanthroline System: Syntheses and Structures

Russian Journal of Coordination Chemistry - The cation-anionic coordination compounds based on the copper(II) complexes with Phen and tartratogermanate anions,...     

Synthesis,Structural Characterization,Thermogravimetric, and Molecular Modelling of Novel Mn(II), Co(II), and Ni(II) Metal Complexes Derived from New Synthesized 4,6-Diaryl-2-oxonicotinonitrile Ligand

Russian Journal of General Chemistry - Novel coordination compounds of Mn(II), Co(II), and Ni(II) with a new 4-(4-chlorocyclohexyl)-2-oxo-6-(thien-2-yl)-1,2-dihydropyridine-3-carbonitrile ligand...     

The decomposition mechanism of new solid-state 4(5)-aminoimidazole-5(4)-carboxamide coordination compounds

Imidazole ring coordination compounds are very useful models to better understand the coordination properties and the reaction mechanisms of biologically important systems. On the basis of previous work, new Co(II)-, Ni(II)- and Cu(II)-4(5)-aminoimidazole-5(4)-carboxamide coordination compounds have been synthesized and characterized by elemental analysis, UV-Vis and IR spectroscopies. Their thermal stability was determined by differential scanning calorimetry and by thermogravimetry, and the decomposition mechanisms were investigated by evolved gas analysis (EGA).     

Application of near infrared spectroscopy for the determination of adsorbed p-nitrophenol on HDTMA organoclay--implications for the removal of organic pollutants from water

NIR spectroscopy has been used to measure the adsorption of p-nitrophenol on untreated montmorillonite and surfactant exchanged montmorillonite. p-Nitrophenol is characterised by an intense NIR band at 8890 cm(-1) which shifts to 8840 cm(-1) upon adsorption on organoclay. The band was not observed for p-nitrophenol adsorbed on untreated montmorillonite. Both the montmorillonite and the surfactant modified montmorillonite are characterised by NIR bands at 7061 and 6791 cm(-1). The organoclay is characterised by two prominent bands at 5871 and 5667 cm(-1) assigned to the fundamental overtones of the mid-IR bands at 2916 and 2850 cm(-1). A band at 6017 cm(-1) is attributed to the p-nitrophenol adsorbed on the organoclay. The band is not observed for the montmorillonite with adsorbed p-nitrophenol. It is concluded that p-nitrophenol is adsorbed to significantly greater amounts on the organoclay compared with the untreated montmorillonite. The implication is that organoclays are most useful for removing organic molecules from water through adsorption.     

聚邻氨基酚膜的络合与再修饰的研究

本文研究了聚邻氨基酚(POAP)膜的络合与再修饰。POAP膜可分离与交换Fe~(2+)、Co~(2+)、Ni~(2+)等第八族元素。POAP-Fe(CN)_6~(3-)膜有稳定的氧化还原电流峰,电位漂移小,重现性好,适合于制成新型参比电极。再修饰的POAP-四氯苯醌具有良好的pH特性。     

Stability of coordination compounds of Co2+ and Ni2+ ions with maleic acid anion in aqueous isopropanol solutions

Composition and stability of coordination compounds of nickel(II) and cobalt(II) ions with maleic acid anion in aqueous isopropanol solutions (H₂O-IPA) of composition χ_IPA = 0–0.5 mole fraction was studied by potentiometric titration at ionic strength of 0.1 maintained with sodium perchlorate at 298.15 K. Monoligand complexes of Ni²⁺ and Co²⁺ ions with maleic acid anion become stronger when isopropanol content rises. In the solvent of the studied composition, Co²⁺ ions form less stable complexes than Ni²⁺ ions that corresponds to the Irving-Williams series established for aqueous solutions. Variations in complex stability are more expressed at small IPA content and differ within experimental error at χ_IPA = 0.5 mole fraction. Obtained results were compared with literature data for akin compounds.     

Stability of Cu(II) and Zn(II) Complexes with Pyridinecarbohydrazones of Pyridoxal-5-phosphate in Aqueous Solution

Composition of coordination compounds formed by copper(II) or zinc(II) ions and pyridine-2-, -3-, and -4-carbohydrazones of pyridoxal-5-phosphate in aqueous solution at 298.2 K, рН 7.4, I 0.25 has been studied by means of spectrophotometry. Conditional constants of the complexes stability have been determined. Cu(II) ions formed more stable ML₂ coordination compounds in comparison with Zn(II), zinc(II) ions are efficiently bound to the derivative of picolinic acid hydrazide to form the ML complex.     

2-甲基喹 淋与Cu(ClO~4)~2和Cu(BF~4)~2生成配合物的结构研究

以2-甲基喹 啉为配体合成了五种含有阴离子ClO~4^-或BF~4^-的铜(II)配合物, 利用元素分析、红外光谱、电子光谱、电导、热重谱、ESR谱及变温磁化率的测定推测了配合物的结构, 提出双核铜配合物中含有直线型单氧桥Cu(II)-O-Cu(II)键的可能构型。     

Coordination Compounds of Cobalt(II), Nickel(II), and Copper(II) Halides with 2-Methyl-1,2,4-Triazolo[1,5-a]benzimidazole

Russian Journal of Coordination Chemistry - New coordination compounds of Co(II), Ni(II), and Cu(II) halides with 2-methyl-1,2,4-triazolo[1,5-a]benzimidazole (L), [Co(L)2Cl2] (Ia),...     

Homo-and heterodinuclear complexes of the tris(catecholamide) derivative of a tetraazamacrocycle with Fe3+, Cu2+ and Zn2+ metal ions

The new ditopic catecholamide 3,7,11-tris-{N-[3,4-(dihydroxybenzoyl)-aminopropyl]} derivative of a 14-membered tetraazamacrocycle containing pyridine (H(6)L(1)) has been synthesized. The protonation constants of (L(1))(6-) and the stability constants of its mono-, homo- and hetero-dinuclear complexes with Fe(3+), Cu(2+) and Zn(2+) metal ions were determined at 298.2 K and ionic strength 0.10 mol dm(-3) in KNO(3). The large overall basicity of the ligand was ascribed to the very high protonation constants of the catecholate groups, and its acid-base behaviour was correlated with the presence of tertiary nitrogen atoms and secondary amide functions. The UV-vis spectrum of the red solution of [FeL(1)](3-) complex exhibits the LMCT band of catecholate to iron(III), and its EPR spectrum revealed a typical isotropic signal of a rhombic distorted ferric centre in a high-spin state and E/D approximately 0.31, both characteristic of a tris-catecholate octahedral environment. The ligand forms with copper(II) and zinc(II) ions mono- and dinuclear protonated complexes and their stability constants were determined, except for the [ML(1)](4-) complexes as the last proton is released at very high pH. Electronic spectroscopic studies of the copper complexes revealed the involvement of catecholate groups in the coordination to the metal centre in the mono- and dinuclear copper(II) complexes. This information together with the determined stability constants indicated that the copper(II) ion can be involved in both types of coordination site of the ligand with comparable binding affinity. The EPR spectrum of [Cu(2)L(1)](2-) showed a well resolved seven-line hyperfine pattern of copper(II) dinuclear species typical of a paramagnetic triplet spin state with weak coupling between the two metal centres. Thermodynamically stable heterodinuclear complexes, [CuFeH(h)L(1)](h-1) (h = 0-3) and [CuZnH(h)L(1)](h-2) (h = 0-4), were formed as expected from a ditopic ligand having two dissimilar coordination sites. At physiological pH, the [CuFeL(1)](-) complex is formed at approximately 100%. The formation of the [CuFeH(h)L(1)](h-1) complexes in solution was supported by electronic spectroscopic measurements. The data indicated the specific coordination of each metal centre at the dissimilar sites of the ligand, the iron(III) bound to the oxygen donors of the catecholate arms and the copper(II) coordinated to the amine donors of the macrocyclic ring. The two metal centres are weakly coupled, due to the fairly large distance between them.     

Interaction of 2-(2'-pyridyl)benzimidazolyl derivative ligands with group 12 metal ions: coordination, structures and luminescence

The coordination chemistry of the group 12 metal ions with two 2-(2'-pyridyl)benzimidazolyl derivative ligands 1,3,5-tris[2-(2'-pyridyl)benzimidazolyl]benzene (tmb) and 2-(2'-pyridyl)benzimidazolylbenzene (mb) has been investigated. The crystal structures of two coordination compounds (HgCl(2))(2)(tmb) and [Zn(mb)(2)(H(2)O)][ClO(4)](2) have been determined by single-crystal X-ray diffraction analysis which established the chelate bonding mode by the group 12 metal ions to the tmb or mb ligand. The luminescent response of tmb and mb toward group 12 metal ions, Zn(II), Cd(II) and Hg(II) has been examined by fluorescent titration experiments which established that the three group 12 metal ions have distinct luminescent response toward the tmb or mb ligand. The addition of the Hg(II) ion resulted in fluorescence quenching. In contrast, the addition of Zn(II) or Cd(II) led to a red shift and dramatic intensity increase of the emission spectrum of the ligand.     

SPIN CROSSOVER IN IRON(II) COMPLEXES WITH TRIS(PYRAZOL-1-YL)METHANE AND [Ag(CN)2]– AND [Au(CN)2]– ANIONS

Journal of Structural Chemistry - New coordination compounds of iron(II) with tris(pyrazol-1-yl)methane (HC(pz)3) containing dicyanoargentate and dicyanoaurate ions of the composition...