Kinetics and Mechanism of the Oxidation of Glycol by Dihydroxyditelluratoargentate(Ⅲ) with Spectrophotometry

The kinetics of the oxidation of glycol by dihydroxyditelluratoargentate (Ⅲ) complex(DDA) was studied in alkaline medium with spectrophotometry(in a temperature range of 16.6-40 ℃).The first-order rates with respect to glycol and Ag(Ⅲ) were all found.The rates increased with the increase in [OH-] and decreased with the increase in [TeO2-4].No effect was found with the addition of KNO3 and no free radical was detected.In view of this,the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can explain all experimental observations.Activation parameters of the rate-determining step and constants are evaluated.     

Synthesis and relaxivity of Gd(Ⅲ), Fe(Ⅲ) and Mn(Ⅱ) complexes with dihydropyridine derivative of diethvlenetriaminepentaacetic acid

A novel ligand of DTPA-dihydropyridine derivative was synthesized by reaction of DTPA-dianhydride with 4-aniline-1,4-dihydropyridine. Its complexes of gadolinium, manganese and iron were prepared. Their spin-lattice relaxivities (T1) were investigated. The results show that the NMR T1 relaxivitives (R1) for complexes of Fe(Ⅲ), Mn(Ⅱ) are less than that of Gd(Ⅲ) complex, which has a high relaxivity (R1) on the surrounding water protons, indicating that the Gd(Ⅲ) complex possesses the precondition to be contrast agents for magnetic resonance imaging.     

Proton Transfer Mechanism of Alanine Induced by Zn~（2＋）： a Theoretical Study

In this paper, proton transfer mechanism of alanine induced by Zn2+ was investiga- ted by the CCSD/6-31++G**//B3LYP/6-31++G** method. Six neutral complexes and one ampho- teric complex were optimized, among which the amphoteric complex was the most stable with binding energy of 201.92 kcal·mol-1. In addition, the rotation of intramolecular single bond leads to the neutral configuration conversion, in which the rotation energy barriers of C–C single bonds are lower than 10.51 kcal·mol-1, and those of C–O single bonds range among 9.53~17.50 kcal·mol-1. On the other hand, the proton transfers among the carboxylic oxygen atoms can also result in the neutral configuration conversion, whose energy barriers of forward/back reaction are 53.90 and 32.46 kcal·mol-1, respectively. In detail, the proton transfers from carboxylic group to amino lead to their configuration conversion from neutral to amphoteric. Furthermore, under the catalysis of Zn2+, there was no energy barrier in this reaction. The conversion route from the most stable neutral configuration Ⅱ to the most stable amphoteric configuration I was: Ⅱ→Ⅱ-Ⅲ→Ⅲ→Ⅲ-Ⅵ→Ⅵ→Ⅴ-Ⅵ→Ⅴ→Ⅰ-Ⅴ→Ⅰ,with the energy barrier to be 64.64 kcal·mol-1.     

OXIDATION OF ALKYLBENZENES CATALYZED BY IRON( Ⅱ,Ⅲ)-1,10-PHENANTHROLINE AND 2, 2''''-BIPYRIDINE COMPLEXES

Oxidation of alkybenzenes PhCH_2R(R=H, CH_3, C_2H_5 and n-C_3H_7) under 1 atm. of O_2 or air catalyzed by iron(Ⅱ, Ⅲ)-2,2'-bipyridine and 1,10-phenanthroline complexes, affords the aryl-substituted ketones and alcohols with the conversion of 15.00％～34.58％ containing of 97.60％～99.80％ ketones and alcohols. The turnover numbers of these catalysts are over 3500 mol-cat. ~(-1)for 3.5 h.     

OLIGOMERIZATION AND POLYMERIZATION OF PERFLUOROALKENES AND PERFLUOROALKYNES CATALYZED BY π-BIS (ARENE) CHROMIUM (0) COMPLEXES

Oligomerization of perfluoropropylene catalyzed by π-bis-(arene)chromium(0) gave two dimers(ⅡA and ⅡB), two trimers(ⅢA and ⅢB) and two defluorotrimers(ⅣA and ⅣB). The last were found to arise from hydrogenation of ⅢB followed by dehydrofluorination. Hydrogen fluoride evolved was added to perfluoropropylene to give 2-hydroheptafluoropropane. By using labeling technique, hydrogen was found to arise from ligand presumably through π-σ rearrangement, A possible mechanism was proposed, π-Bis(benzene)chromium(0) was able to catalyze the polymerization of perfluorobut-2-yne to form its polymer, a white powder. The same catalyst could catalyze copolymerization of CF_3CCCF_3 and CF3CFCF_2 to give solid copolymer. Three perfluoro-2-alkynenitriles (CF_3CC-CN,C_2F_5CC-CN, n-C_3F_7CC-CN) were successfully synthesized by intramolecular Wittig reaction and one of them, i.e, C_2F_5C CCN was polymerized catalytically by π-bis(benzene)chromium(0) to give its polymer. a black powder.     

Synthesis and Magnetic Properties of Copper (Ⅱ) Complexes with Pyridine N-Oxide-2-ylmethy-lidenedithiocarbazate as Ligands

A series of copper (Ⅱ) complexes with pyridine N- oxide- 2- ylmethylidened-ithiocarbazates as ligands were synthesized and characterized by IR spectra, electronic spectra and magnetic moments measurement at room temperature. Variable temperature magnetic susceptibilites (3-300K) of four complexs were measured and fitted with the Bleaney-Bowers dimer equation by considering the magnetic interaction between molecules. The fitting results show the existence of intramolecular ferromagnetic interactions and intermolecu-lar anti-ferromagnetic interactions in these copper( Ⅱ) complexes.     

Electrochemical Co-reduction of Bi(Ⅲ)and Y(Ⅲ)and Extracting Yttrium from Molten LiCl-KCl Using Liquid Bi as Cathode

The electrochemical reaction of Bi(Ⅲ)and co-reduction behaviour of Bi(Ⅲ)and Y(Ⅲ)ions were researched in molten LiCl-KCl on a ttmgsten(W)electrode employing a range of electrochemical teclmiques.Cyclic voltammetric and square-wave voltanunetric results revealed that the reduction of Bi(Ⅲ)was a one-step process,with the exchange of three electrons on a W electrode,and diffusion-controlled.The electrochemical curves showed two reduction peaks pertaining to the formation of Bi-Y alloy compounds,because of the co-reduction of Bi(Ⅲ)and Y(Ⅲ) by metallic Y deposited on the pre-deposited Bi-coated W electrode and reacting with Bi metal in molten LiCl-KCl. Furthermore,galvanostatic electrolysis was conducted using liquid Bi as cathode to extract yttrium at different current intensities,and the extractive products were analyzed by SEM,EDS and XRD.The results indicated that BiY intermetallic compotmd was formed in the molten LiCl-KCl-YCl3 system.     

Theoretical Study on the Inclusion Complex of β-Cyclodextrin and Nitrobenzene

Quantum chemical calculations were carried out to investigate the structures and properties for the inclusion complexes of nitrobenzene (NB) into β-cyclodextrin. Two low-energy conformations of β-cyclodextrin (A and B) in the gas phase were initially investigated by the PM3 and B3LYP/6-31+G(d,p) calculations, respectively. Three different orientations were considered in the inclusion process of A and B with NB to form 1:1 complexes. Potential energy scan by PM3 calculations indicated that the phenyl orientation Ab for conformation A and the equator orientation Bc for conformation B are more favorable in energy, respectively. We also considered the 2:1 inclusion complexes of host A or B with guest NB in the gas phase. PM3 calculation indicated that the host-guest interaction energies to form 1:1 complexes are more negative than those to form 2:1 NB/B complexes. Finally, we studied the solvent effect of NB/CD complex, and PM3 results show that the influence of water molecules on the inclusion process is very important. The driving forces for the inclusion process and the geometries of complexes were discussed in detail.     

Theoretical studies on the complexation of Eu(Ⅲ) and Am(Ⅲ) with HDEHP: structure,bonding nature and stability

Separation of trivalent lanthanides(Ln(Ⅲ)) and actinides(An(Ⅲ)) is a key issue in the advanced spent nuclear fuel reprocessing. In the well-known trivalent actinide lanthanide separation by phosphorus reagent extraction from aqueous komplexes(TALSPEAK) process, the organophosphorus ligand HDEHP(di-(2-ethylhexyl) phosphoric acid) has been used as an efficient reagent for the partitioning of Ln(Ⅲ) from An(Ⅲ) with the combination of a holdback reagent in aqueous lactate buffer solution. In this work, the structural and electronic properties of Eu~(3+) and Am~(3+) complexes with HDEHP in nitric acid solution have been systematically explored by using scalar-relativistic density functional theory(DFT). It was found that HDEHP can coordinate with M(Ⅲ)(M=Eu, Am) cations in the form of hydrogen-bonded dimers HL_2~-(L=DEHP), and the metal ions prefer to coordinate with the phosphoryl oxygen atom of the ligand. For all the extraction complexes, the metal-ligand bonds are mainly ionic in nature. Although Eu(Ⅲ) complexes have higher interaction energies, the HL_2~- dimer shows comparable affinity for Eu(Ⅲ) and Am(Ⅲ) according to thermodynamic analysis, which may be attributed to the higher stabilities of Eu(Ⅲ) nonahydrate. It is expected that this work could provide insightful information on the complexation of An(Ⅲ) and Ln(Ⅲ) with HDEHP at the molecular level.     

Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate（Ⅲ）in Alkaline Medium

The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ）[abbreviated as DDA of Ag(Ⅲ）]anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25-40℃.The order of the redox reaction of lactic acid and DDA was found to be first-order.The rates increased with the increase in [OH^-]and decreased with the increase in [tellurate].No free radical was detected.In the view of this the dihydroxymonotelluratoargentate(Ⅲ）species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can be used to explain all the experimenttal results.The activation parameters(25℃）and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.     

Bis(1-(4-(dimethylamino)benzylidene)-4-phenylthiose micarbaznato)palladium(Ⅱ):Synthesis,Crystal Structure and Its Dual Fluorescence Property

The title compound bis(1-(4-(dimethylamino)benzylidene)-4-phenylthiosemicar-bazato)-palladium(Ⅱ)(PdL2) was obtained by reacting 1-(4-(dimethylamino)benzylidene)-4-phenyl-thiosemicarbazide with dichlorobis(benzonitrile)palladium(Ⅱ) in methanol,and its structure was characterized by single-crystal X-ray diffraction.The crystal of PdL2 was obtained in dimethyl-formamide(DMF) solvent with solvent molecules involved in the cell and crystallizes in the monoclinic system,space group C2 with a = 18.485(15),b = 7.090(5),c = 17.595(11) ,β = 121.21(3)o,V = 1972(2) 3,Z = 2,Mr = 847.40,Dc = 1.427 g/cm3,μ = 0.624 mm-1,F(000) = 880,R = 0.0607 and wR = 0.1358.The Pd atom adopts a distorted square planar coordination geometry with two Pd-N and two Pd-S bonds.The ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via mercapto sulfur and the imine nitrogen atom,which binds to palladium as bidentate N,S-donors forming five-membered chelate rings.The complex formed hydrogen bonding interaction with solvent DMF molecules from the hydrogen of phenylamine to the oxygen of DMF and several intramolecular hydrogen bonds.Pd(Ⅱ) perturbed ligand π-π* transition and metal-to-ligand charge transfer(MLCT) transition are observed in its electronic absorption spectra.The complex exhibits intraligand 1π-π*(IL) state and MLCT state dual fluorescent emissions in organic solvent at room temperature.     

Kinetic study on the ligand exchange reactions between bis(alkylxanthato)palladium(II)and bis(N,N-dialkyldithiocarbamato)palladium(II)by high-performance liquid chromatography

The rate constants and equilibrium constants of ligand exchange reactions between his(alkylxanthato)palladium(Ⅱ),Pd(S_2COR)_2(R=Am,n-Hex,Bz),and bis(N,N-dialkyldithiocarbamato)palladium(Ⅱ),Pd(S_2CNR_2)_2(K=Et,n-Pr,n-Bu),in chloroform solution have been determined ina temperature range of 20—50°C by means of high-performance liquid chromatography.It was foundthat both the forward and reverse reactions are of second order.All of the equilibrium constants Kdetermined are 10.3±1.0,much greater than the value(K=4)calculated statistically which indicatesthat the ternary complexes are more stable than the binary complexes.The experimental resultsrevealed that the reaction rate decreases with the increase in the size of R and R~1 groups and the latterare more remarkable,consistent with the deduction of steric effect.The activation parameters ofthe reactions have been calculated.In reaction series(11)and(12)(in the text)the isokinetic tempera-tures B=390±8K and β=346±15 K have been observed respectively.A plausiblemechanism in-volving an eight-membered ring intermediate has been proposed on the basis of experimental results.     

Synthesis and catalytic activity of novel heteronuclear Ln(Ⅲ)-Cu(Ⅱ) complexes with noncyclic polyether-amino acid Schiff base

A series of novel heteronuclear Ln(Ⅲ)-Cu(Ⅱ) complexes with noncyclic polyether-amino acid Schiff base were synthesized. The general formula is [LnCu_2(H_2TALY)(NO_3)_5](NO_3)_2' nH_2O(Ln=La, Nd, Sm, Gd, n= 4; Ln=Yb, Y, n=3), where H_2TALY = tetraglycol aldehyde bis-lysine Schiff base. It is the first time to report the synthetic method for this new Cu(Ⅱ) complexes and Ln(Ⅲ)-Cu(Ⅱ) heteronuclear complexes. The complexes were characterized by elemental analysis, IR spectra, TG-DTA, magnetic susceptibility, and especially by a 500 MHz NMR spectrometer for 2D-COSY NMR. Coordination mechanism and structures of complexes have been suggested as well. Of particular interest is the potential that the novel complexes obtained may be used as a catalyst, which prompted us to investigate them. It shows 100% conversion with the viscosity-average molecular weight 120 000 for the polymerization of methyl methacrylate (MMA) without addition of any cocatalyst. Furthermore, the complexes with such aliphatic Schiff bas     

Synthesis, Characterization and Weak Intramolecular Interactions of Porphyrins Bearing Nucleobases

5,10, 15-Triphenyl-20-{2- [α- (adenine-9 ) acetylamino]} phenyl porphyrin ( 1 ), 5,10, 15-triphenyl-20-{2-[α-(cytosine-1)acetylamino]} phenyl porphyrin (2), 5, 10, 15-triphenyl-20-{4-[α-(cytosine-1)ethoxy]} phenyl porphyrin (3) and their zinc complexes Zn-1, Zn-2 and Zn-3 have been prepared and characterized by ^1H NMR spectra, elemental analyses, electronic absorption spectra and mass spectra (FAB). Intramolecular π-π interactions and intramolecular metal-~ interaction for 1, 2, Zn-1,and Zn-2 have been investigated by several methods. ^1H NMR studies demonstrate that the porphyrin π-system in 1 and 2 is parallel to the adenine and the cytosine aromatic ring, respectively. The electronic absorption spectral properties of free porphyrin derivatives and their zinc complexes have been compared with those of H2TPP and ZnTPP. The results show that the UV-vis spectra of 1 and 2 are the same as that of H2TPP,whereas the spectra of their zinc complexes show 7 nm red shifts of the Soret bands compared to that of ZnTPP. The emission spectra of Zn-1 and Zn-2 are independent of excitation wavelength. From combination of the evidence of absorption and emission spectra it is suggested the existence of intramolecular metal-π interaction in Zn-1 and Zn-2. The results of conformational analysis agreed quite nicely with that of experiments, thus it was further to validate the experimental conclusions.     

Synthesis,characterization and magnetism of copper(Ⅱ)-lan-thanide(Ⅲ) heterobimetalic complexes with N,N'-oxamidobis-(benzoato) cuprate (Ⅱ)

Seven new μ-oxamido copper(Ⅱ)-lanthanide(Ⅲ)hetero-bitnetalic complexes described by the fonnula Cu(obbz)Ln-(Ph-phen)2NO3(Ln=La,Nd,Eu,Gd,Tb,Ho,Er),where obbz denotes the oxamidobis(benzoato)and Ph-phen represents 5-phenyl-1,10-phenanthroline,have been synthesized and characterized by the elemental analyses,spectro-scopic(IR,UV,ESR)studies,magnetic moments(at room temperature)and molar conductivity measurement.The temperature dependence of the magnetic susceptibility of Cu(obbz)Gd(Ph-phen)2NO3 complex has been measured over the range 4.2-300 K.The least-squares fit of the experimental susceptibilities based on the spin Hamiltonian operator,H=-2JS1 S2,yielded J= 1.28 cm-1,a weak ferromagnetic coupling.A plausible mechanism for a ferromagnetic coupling between Gd(Ⅲ)-Cu(Ⅱ)is discussed in terms of spin-polarization.     

Kinetics and Mechanism of Oxidation of Glycol by Dihydroxydiperiodatonickelate ( Ⅳ )Complex in Aqueous Alkaline Medium

The kinetics of oxidation of glycol by dihydroxydiperiodato nickelate ( Ⅳ) complex (DDN) was studied by spectrophotometry in aqueous alkaline medium in a temperature range of 25-40℃. The reaction was found to be first order with respect to Ni( Ⅳ ) and also to be first order with respect to glycol. The rate increases with the increase in [OH ] and decreases with the increase in [IO-4], showing that dihydroxymonoperiodatonickelate ( Ⅳ )(DMN) is the reactive species of oxidant. Salt effect indicated that the reaction is of ion-dipole type. No free radical was detected. A mechanism of an inner-sphere two-electron transfer reaction involving a preequilibrium between DDN and DMN is proposed, and the rate equation derived from the mechanism can explain all experimental observations. Activation parameters of the rate-determing step and the equilibrium constants were calculated.     

A simple kinetic model for oxidative coupling of methane over La_(0.6)Sr_(0.4)Co_(0.8)Fe_(0.2)O_(3-δ) nanocatalyst

A simplified kinetic model for the oxidative coupling of methane over a La0.6Sr0.4Co0.8Fe0.2O3-δ nanocatalyst is presented. The kinetic model was developed by experimental data in a catalytic micro-reactor covering a wide range of reaction conditions (0.04相似文献   

Vibrational Spectroscopic Study of （E）-3-（4-fluorophenyl）-N-[4-（phenylamino） quinazoline-7-yl] Acrylamide

Geometry optimization and subsequent harmonic vibration calculations of prior synthesized (E)-3-(4-fluorophenyl)-N-[4-(phenyl-amino) quinazoline-7-yl] acrylamide were carried out by DFT/B3LYP method with both 6-31G and 6-311G basis sets.The Infrared (IR) spectrum of the title compound was recorded in the field of 400-4000 cm 1 and then assigned.The correlation analyses between the scaled theoretical vibration frequencies and the experimental ones indicate that there exist good linearity relationships since the correlation coefficients R 2 are larger than 0.999.The intramolecular interactions existed in the title molecule were confirmed by the Atoms in molecules (AIM) method,and their influences on the absorption frequency were also investigated.     

PREPARATION AND CHARACTERIZATION OF NOVEL CHITOSAN DERIVATIVES: ADSORPTION EQUILIBRIUM OF IRON(Ⅲ) ION

The adsorption of Fe(Ⅲ)ions from aqueous solution by chitosan alpha-ketoglutaric acid(KCTS)and hydroxamated chitosan alpha-ketoglutaric acid(HKCTS)was studied in a batch adsorption system.Experiments were carried out as function of pH,temperature,agitation rate and concentration of Fe(Ⅲ)ions.The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and isotherm constants were determined.The Langmuir model agrees very well with experimental data.The pseudo-first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated.The dynamical data fit well with the second-order kinetic model.The pseudo second-order kinetic model was indicated with the activation energy of 19.61 and 7.98 kJ/mol for KCTS and HKCTS,respectively.It is suggested that the overall rate of Fe(Ⅲ)adsorption is likely to be controlled by the chemical process.Results also showed that novel chitosan derivatives(KCTS and HKCTS)were favorable adsorbents.     

Improvement on stability of square planar rhodium (Ⅰ) complexes for carbonylation of methanol to acetic acid

A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces the investment on the equipment.