Kinetics and stoichiometry of the reaction between ozone and C70 fullerene in CCl4

The kinetics and stoichiometry of the reaction between C₇₀ fullerene and ozone have been studied. The reaction obeys a bimolecular rate law. The stoichiometric coefficients of the reaction are 1: 12 to 1: 22, depending on reaction conditions. The rate constant at 22°C is 5 × 10⁴ l mol^?1 s^?1 for the first stage of fullerene conversion and (0.8–0.6) × 10⁴ l mol^?1 s^?1 for the subsequent stages. Since the stages differ in terms of reaction rate, the original C₇₀ molecules are first involved in the reaction, whereas, at the subsequent stages, all molecules are involved with equal probabilities, irrespective of the number of preceding reaction events in which they have participated.     

Photoinitiated reactions of allyltriorgano-silanes and -germanes with polyhaloidalkanes. Study of the mechanisms of the reactions by means of the 1H CIDNP method

The radical stages in the photolysis reactions of various allyltriorgano-silanes and -germanes (R₃MCH₂CHCH₂; M = Si, Ge) with polyhaloidalkanes have been studied using the ¹H CIDNP method. It has been shown that the mechanism of the photochemical reaction for M = Sn, Ge is different from the case when M = Sn. Some rather stable R₃MCH₂CH(Hal)CH₂R′ (M = Si, Ge) derivatives were isolated and characterized.     

The cationic dimerization of 1,1-diphenylethylene. III. Kinetics of initiation by aluminum chloride

Kinetics of the reaction of AlCl₃ with 1,1-diphenylethylene (DPE) in CH₂Cl₂ solution have been investigated at low temperature by ultraviolet (UV) spectrophotometry. Initiation proceeds in three successive stages. The first, very fast and leading to a low and constant concentration of carbocations, is assigned to residual traces of cocatalyst. A second stage, slower but more extensive, yields about one carbocation for two aluminum in a reaction that is first order in AlCl₃ and first order in monomer (k_i = 2.5 10^?2 liter mole^?1 sec^?1 at ?30°; E_i = 10 kcal mole^?1). This stage, which takes place after consumption of residual cocatalyst, should be attributed to a direct initiation. In a proposed mechanism the cationic intermediate produced by reaction of DPE with AlCl₃ transfers a proton to DPE, thus leading to a stable diphenylethyl cation and to alkenyldichloroaluminum (Al-Cl₂CH?CPh₂). A third stage develops slowly and the yield in carbocations finally reaches 65–70% with respect to AlCl₃. This stage is tentatively assigned to a second direct initiation by the less active organoaluminum compound formed in the preceding stage.     

Determination of complex forming conditions of 8-hydroxyquinoline with technetium-99m

Complex forming conditions of 8-hydroxyquinoline with^99mTc have been specified.^99mTcO₄ ^– has been reduced by SnCl₂ to a lower oxidation level. Labeling yields have been determined by ITLC (Instant Thin Layer Chromatography). Various parameters, such as pH, temperature, reaction time, ligand to SnCl₂ ratio, which can affect the labeling yields, have been determined. Optimum conditions are 4–7 for pH; 15–20°C (room) for temperature; 1.55 for ligand to SnCl₂ ratio and 5 min for reaction time.     

Friedel-crafts copolymerization of thiophene and p-di(chloromethyl)benzene. I. Products,kinetics, and mechanism of the early stages of the reaction

The rate of polymerization of thiophene, at concentrations of catalyst (SnCl₄), and thiophene of the same order as was subsequently used in studying the reaction between thiophene and di(chloromethyl)benzene, is of the order of 10^-2%/hr at 30°C. There is no significant self-condensation of DCMB under the same conditions. Since the reaction between thiophene and DCMB is complete at 30°C in minutes rather than hours, it is assumed that self-condensation of thiophene or DCMB during the reaction between them will be negligible and should not influence the course of the reaction or the structure of the resulting polymer. Reaction at 30°C is much too fast for convenient study. A temperature of 0°C is more appropriate and was used in subsequent kinetic work. The first two products of the condensation of p-di(chloromethyl)benzene (DCMB) with thiophene have been identified by a combination of mass, infrared, and nuclear magnetic resonance spectroscopy as thenylchloromethylbenzene (TCMB) and dithenylbenzene (DTB). DCMB, TCMB, and DTB have been estimated quantitatively during the course of the reaction by gas-liquid chromatography (GLC), and it has been established that the rates of each of the two reaction steps is first-order with respect to the chloro compound (DCMB and TCMB respectively), thiophene, and SnCl₄. Rate constants for these two consecutive reactions were calculated to be k₁ = 2.79 × 10^-4l.²/mole²-sec, k₂ = 6.37 × 10^-3l.²/mole²-sec; the corresponding energies of activation are E₁ = 7.93 kcal/mole, E₂ = 7°67 kcal/mole. These rate constants are appreciably higher than values previously obtained for the corresponding DCMB–benzene reactions.     

The oxidation of organic substances by compounds of trivalent manganese: XIV. Oxidation of malonic acid by manganese(III) sulfate in sulfuric acid medium and with hexaquomanganese(III) ions in noncomplexing perchloric acid medium

The oxidation of malonic acid by manganese(III) sulfate in a medium of sulfuric acid and by hexaquomanganese(III) ions in a noncomplexing perchloric acid medium was studied.The reaction stoichiometry was found and the effect of the concentrations of H⁺, Mn²⁺, and HSO₄^? ions and of the initial reactant concentrations on the course and rate of the reaction was studied.The optimum conditions have been found for analytical use of the reaction, procedures have been proposed for the determination of malonic acid using the two reagents, and the accuracy and reproducibility of the determinations have been found.     

A Novel Process for CO2 Capture by Using Sodium Metaborate,Part II: Carbonation Reaction and Kinetic Studies

In Part II of this two‐part series of papers, optimization of carbonation reaction with sodium metaborate and kinetics of the reaction are studied and compared to the structural properties, which were reported in Part I. This paper presents a comprehensive study on the optimization of reaction conditions and determination of reaction parameters of sodium metaborate (NaBO₂) and carbon dioxide (CO₂). Both hydrated and dehydrated forms of NaBO₂ have high sorption capacities of CO₂ up to 400°C. Decomposition of the products starts beyond 400°C and completes at 600°C. The shrinking core model is used to explain the kinetics of the noncatalytic heterogeneous reaction. The reaction progresses in two stages: one is surface reaction controlled and the other is diffusion controlled. The apparent activation energy and preexponential factor for reaction‐controlled and diffusion‐controlled regions are calculated as 11.8 kJ/mol and 3.5 × 10⁶ cm²/min and 18.2 kJ/mol and 6.5 × 10⁻⁵ cm²/min, respectively.     

High-throughput syntheses of iron phosphite open frameworks in ionic liquids

Three open-framework iron phosphites: Fe^п₅(NH₄)₂(HPO₃)₆ (1), Fe^п₂Fe^♯(NH₄)(HPO₃)₄ (2) and Fe^♯₂(HPO₃)₃ (3) have been synthesized under ionothermal conditions. How the different synthesis parameters, such as the gel concentrations, synthetic times, reaction temperatures and solvents affect the products have been monitored by using high-throughput approaches. Within each type of experiment, relevant products have been investigated. The optimal reaction conditions are obtained from a series of experiments by high-throughput approaches. All the structures are determined by single-crystal X-ray diffraction analysis and further characterized by PXRD, TGA and FTIR analyses. Magnetic study reveals that those three compounds show interesting magnetic behavior at low temperature.     

Methane Activation by Diatomic Molybdenum Carbide Cations

Metal carbide species have been proposed as a new type of chemical entity to activate methane in both gas‐phase and condensed‐phase studies. Herein, methane activation by the diatomic cation MoC⁺ is presented. MoC⁺ ions have been prepared and mass‐selected by a quadrupole mass filter and then allowed to interact with methane in a hexapole reaction cell. The reactant and product ions have been detected by a reflectron time‐of‐flight mass spectrometer. Bare metal Mo⁺ and MoC₂H₂⁺ ions have been observed as products, suggesting the occurrence of ethylene elimination and dehydrogenation reactions. The branching ratio of the C₂H₄ elimination channel is much larger than that of the dehydrogenation channel. Density functional theory calculations have been performed to explore in detail the mechanism of the reaction of MoC⁺ with CH₄. The computed results indicate that the ethylene elimination process involves the occurrence of spin conversions in the C?C coupling (doublet→quartet) and hydrogen atom transfer (quartet→sextet) steps. The carbon atom in MoC⁺ plays a key role in methane activation because it becomes sp³ hybridized in the initial stages of the ethylene elimination reaction, which leads to much lower energy barriers and more stable intermediates. This study provides insights into the C?H bond activation and C?C coupling involved in methane transformation over molybdenum carbide‐based catalysts.     

CEPA Calculations of potential energy surfaces for open-shell systems. II. The reaction of C+ Ions with molecular hydrogen

Ab initio calculations including electron correlation effects (mainly on CEPA-PNO level) have been performed for the potential energy surface (PES) of the reaction of ²P carbon ions with molecular hydrogen. For the collinear abstraction reactions (C_∞v symmetry: ²σ⁺, ²Π-2) the minimum energy paths have been determined. The vertical insertion reaction (C_2v; ²A₁,B₁, ²B₂) has been investigated with particular emphasis (minimum energy path, barrier heights, intersystem crossing). The influence of the size of the orbital basis and of electron correlation has been studied in some detail. The interaction of the ²A₁, and ²B₂ surfaces has been analyzed, leading to the conclusion that close to C_2v symmetry a low energy path exists by which CH₂⁺(²A₁)can be easily formed, with a barrier (²B₂ → ²A₁) ≈ 18 kcal/mol below the asymptote. The analysis of electron correlation effects reveals that it is compulsory to correlate the whole valence shell if one wants to obtain reliable surfaces. The influence of singly excited configurations for getting the correct behaviour of the PES is generally small.     

Solid-state decomposition studies on fluoroperoxo species of transition metals. Part VI. Kinetics of isothermal decomposition of M2Zr2(O2)2F6 · 2 H2O (M = Rb+, or Cs+)

The decomposition of solid fluoroperoxozirconates of alkali metals, M₂Zr₂(O₂)₂F₆ · 2 H₂O (M = Rb⁺, Cs⁺), is carried out in vacuum under isothermal conditions. The stoichiometry of the reaction may be represented by the equation, M₂Zr₂(O₂)₂F₆ · 2 H₂O(S) — M₂Zr₂O₂F₆(s) + O₂(g) + 2 H₂ O(g) (condensed). The fractional decomposition α is determined by measuring the pressure of oxygen evolved during pyrolysis with a McLeod gauge. The α values range from 0.06 to 0.70 for the rubidium and from 0.06 to 0.79 for the caesium species in the temperature ranges 107–202°C and 101–219°C, respectively. The α—time data for both compounds show that the kinetics are deceleratory throughout the course of the decomposition reaction. In both compounds, the initial stages of decomposition are described by a unimolecular decay law, while the later stages obey a contracting volume equation at all temperatures. The activation energies from Arrhenius plots are 14.0 and 10.9 kcal mole^?1 for the rubidium and 12.9 and 11.2 kcal mole^?1 for the caesium compound.     

Efficient,Convenient and Mild Three‐Component Template Preparation and Characterization of Some New Schiff Base Complexes

A few kinds of novel Schiff base complexes have been prepared by three‐component reaction of the substituted hydroxyacetophenone with several aliphatic diamines and transition metals such as; Cu(II), Co(II), Mn(II), Zn(II) and UO₂(II) under mild reaction conditions. The products have been afforded with excellent yields and appropriate reaction times. The structures of these ligands have been characterized by their IR, ¹H NMR, ¹³C NMR and MS spectral and physical data.     

Efficient,Convenient and Mild Three Component Template Preparation and Characterization of Some New Schiff Base Complexes

A few kinds of novel Schiff base complexes have been prepared by three component reaction of the substituted hydroxyacetophenone with several aliphatic diamines and transition metals such as; Ni(II), Zn(II) and UO₂(II) under mild reaction conditions. The products have been afforded with excellent yields and appropriate reaction times. The structure of these ligands has been characterized by their IR, ¹H NMR, ¹³C NMR and MS spectral and physical data.     

Microwave synthesis,spectral studies,antimicrobial approach,and coordination behavior of antimony(III) and bismuth(III) compounds with benzothiazoline

The reaction of 2-hydroxy-N-phenylbenzamide with 2-aminobenzenethiol yielded 2-hydroxy-N-phenylbenzamidebenzothiazoline (H₂-Saly · BTZ/HO⋂N⋂SH). The reaction of H₂-Saly · BTZ with PhSbCl₂, SbCl₃, and BiCl₃ under varied reaction conditions (microwave, as well as conventional method) gave corresponding antimony( III) and bismuth(III) Schiff base compounds (substitution along with addition) in different coordination environments. These complexes were characterized by elemental analysis, IR and NMR (¹H and ¹³C) spectral studies. The ligand was found to bifunctional tridentate, as well as monodentate for different starting materials of metal (Sb/Bi), as well as for different reaction conditions, hence, suitable coordination environments and pseudotrigonal bipyramidal geometry for the antimony and bismuth complexes have been proposed. Their biological activities have also been checked against many fungi and bacteria. The complexes were found to be more toxic than the corresponding ligand. The article is published in the original. The article is published in the original.     

Factorial design evaluation of the Suzuki cross-coupling reaction using a magnetically recoverable palladium catalyst

A magnetically recoverable catalyst [Fe₃O₄@SiO₂-AEAPTMS-Pd(II)] was prepared, fully characterized and had its catalytic activity evaluated on the Suzuki cross-coupling reaction under microwave irradiation. The reaction conditions for the synthesis of biaryl compounds was optimized in two stages - an initial fractional design 2⁴, in which the parameters reaction time, temperature, solvent and catalyst loading were evaluated, followed by a Doehlert design. The factorial design proved to be a viable approach for obtaining the optimal reaction conditions based on a relatively small number of experiments. Additionally, the biaryl derivatives synthesized by this method were obtained with good to excellent yields (71–96%) and the recovery and reuse of the palladium catalyst was also evaluated.     

Copper(I)-anilide complex [Na(phen)3][Cu(NPh2)2]: an intermediate in the copper-catalyzed N-arylation of N-phenylaniline

Complex [Na(phen)₃][Cu(NPh₂)₂] ( 2 ), containing a linear bis(N‐phenylanilide)copper(I) anion and a distorted octahedral tris(1,10‐phenanthroline)sodium counter cation, has been isolated from the catalytic C? N cross‐coupling reaction with the CuI/phen/tBuONa (phen=1,10‐phenanthroline) catalytic system. Complex 2 can react with 4‐iodotoluene to produce 4‐methyl‐N,N‐diphenylaniline ( 3 a ) with 70.6 % yield. In addition, 2 can work as an effective catalyst for C? N coupling under the same reaction conditions, thus indicating that 2 is the intermediate of the catalytic system. Both [Cu(NPh₂)₂]^? and [Cu(NPh₂)I]^? have been observed by in situ electron ionization mass spectrometry (ESI‐MS) under catalytic reaction conditions, thus confirming that they are intermediates in the reaction. A catalytic cycle has been proposed based on these observations. The molecular structure of 2 has been determined by single‐crystal X‐ray diffraction analysis.     

Novel nitrogen ligands based on imidazole derivatives and their application in asymmetric catalysis

Recently prepared chiral amines have been used in the preparation of novel tridentate ligands based on an imidazole ring with an additional (hetero)ring. The synthesis was carried out by the reaction of chiral amines with suitable aldehydes (2-phenylimidazole-4-carbaldehyde, 2-hydroxybenzaldehyde or pyridine-2-carbaldehyde) under reductive conditions (H₂/Pd or NaBH₄). All ligands prepared showed strong hydrogen bonds in d₆-DMSO solution, which resulted in hindered imidazole tautomerism. The observed hindered tautomerism was studied by ¹H NMR spectroscopy. The structures of the prepared ligands were also confirmed by APCI mass spectroscopy. Both chiral amines and tridentate compounds have been applied as ligands in copper (II)-catalyzed nitroaldol reactions (Henry reaction). Various reaction conditions for the Henry reaction have been studied (influence of temperature, molar ratio, solvent or copper (II) precursors). The compounds prepared with the two imidazole rings showed fast reaction times and a reversal in enantioselectivity compared to other chiral amines.     

Kinetics of oxidative degradation of pantothenic acid by cerium(IV) in aqueous perchloric acid

The kinetics of oxidation of pantothenic acid (PA), Me₂C(CH₂OH)CH(OH)C(O)NHCH₂CH₂CO₂H, by cerium(IV) in aqueous HClO₄ medium at constant ionic strength, 2.0 mol dm^–3, has been studied spectrophotometrically. The reaction showed first-order kinetics in Ce^IV concentration, an apparent less than unit order dependence in [PA] and an inverse fractional order in [H⁺]. Initial addition of products had no significant effect on the rate of the reaction. A possible mechanism is proposed, and the reaction constants involved in the mechanism have been computed. There is good agreement between the observed and calculated rate constants under different experimental conditions. The activation parameters were calculated with respect to the slow step of the proposed mechanism.     

Kinetics of the reaction between 1,3-diphenylisobenzofuran and nitrogen dioxide studied by steady-state fluorescence

1,3-Diphenylisobenzofuran (DPBF) is a fluorescent molecule which is believed to react highly specifically toward reactive oxygen species such as singlet oxygen (¹O₂), hydroxy (HO^·), alkyloxy (RO^·), and alkylperoxy (ROO^·) radicals. In all cases the reaction product is 1,2-dibenzoylbenzene. In order to prove that DPBF gives the same product in contact with reactive nitrogen species, its reaction with nitrogen dioxide radical has been studied in 2,2,4-trimethylpentane using the steady-state fluorescence method and mass spectrometry. The progress of the studied reaction was measured by observation of changes in fluorescence intensity of DPBF after addition of nitrogen dioxide (NO₂). The rate constants of DPBF fluorescence decay affected by NO₂ have been determined. Experiments were conducted over the temperature range of 13–37 °C and for NO₂ concentrations from 0.02 to 0.14 mmol dm^?3. It has been found that the reaction between 1,3-diphenylisobenzofuran and nitrogen dioxide proceeds in two steps. The first step is a very rapid reaction whose rate could not be measured under established experimental conditions. The second step is slower. The reaction product was identified by registration of mass spectra. The probable reaction mechanism is proposed.     

Radiochemical study of gas-phase reactions of diethylstannyl cations Et2SnT+ with oxygen-containing compounds: II. Reaction of diethylstannyl cations with butanol

Gas-phase reaction of nucleogenic diethylstannyl cations Et₂SnT⁺ with butan-1-ol has been studied by the radiochemcal method, and probable reaction mechanisms have been proposed. During the process diethylstannyl cations undergo isomerization into tertiary Me₂EtSn⁺ cations and rearrangement with elimination of ethane. Thermochemical parameters of reactions of diethyl-substituted cations derived from Group 14 elements (Et₂TM⁺; M = C, Si, Ge, Sn) with alcohols have been analyzed by the M06L aug-cc-pVDZ quantum chemical method.