Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full factorial design analysis

The synthesis of neodymium(III) bromide (NdBr₃) by sintering brominating of neodymium oxide (Nd₂O₃) with ammonium bromide (NH₄Br) was investigated. The influence of various synthesis parameters (temperature, contact time and stoichiometry) on the reaction yield was studied and optimized. The main interaction effects of the synthesis parameters on the reaction yield were also determined by a full 2³ factorial designs with six replicates at the center point.This study showed that the optimum conditions for the synthesis of NdBr₃ are following: contact time t = 60 min, stoichiometry in moles Nd₂O₃:NH₄Br = 1:24 and temperature T = 400 °C. The reaction yield for these parameters was equal to 97.80%. The first order model was obtained to predict the reaction yield as a function of these three parameters. It was shown that all parameters have a significant positive influence on reaction yield. In addition it was pointed out also that the interaction effects between them are significant.     

Insight into the mechanism of diazocompounds transformation catalyzed by hetero cuboidal clusters [Mo3CuQ4(MeBPE)3X4]+, (Q = S,Se; X = Cl,Br): The catalytically active species

Two enantiomerically pure trinuclear compounds of formula (P)-[Mo₃S₄{(R,R)-Me–BPE}₃Br₃]Br and (P)-[Mo₃Se₄{(R,R)-Me–BPE}₃Cl₃]Cl, (P)-1b.Br and (P)-1c.Cl, respectively, have been synthesized in a good yield and a stereospecific manner by excision of polymeric [Mo₃Q₇X₄]_n (Q = S or Se, X = Cl or Br) phases with (R,R)-Me–BPE{1,2-bis[(2R,5R)-2,5-(dimethylphospholan-1-yl)]ethane}. They have been transformed into chiral hetereo cuboidal compounds [Mo₃S₄{(R,R)-Me–BPE}₃Br₃]PF₆, (P)-2b.PF₆, and [Mo₃Se₄{(R,R)-Me–BPE}₃Cl₃]PF₆, (P)-2c.PF₆, by reaction with copper salts. All these compounds have been characterized by ³¹P NMR, IR, UV–Vis, mass spectrometry, elemental analysis, and chiral dichroism. The catalytic potential of tetranuclear cuboidal compounds has been assessed in the paradigm intermolecular cyclopropanation reaction of styrene with ethyl diazoacetate. Results are compared with those obtained for the analogue [Mo₃S₄{(R,R)-Me–BPE}₃Cl₃]PF₆, (P)-2a.PF₆. The catalytic data demonstrate that the Se derivative (P)-2c.PF₆ is less reactive than the S analogues, but it leads to a similar product distribution as the sulfide analogue (P)-2a.PF₆. By contrast, exchange of chlorine by the bulky bromine gives rise to a catalyst which makes the carbene dimerization more competitive. These data agree with temporal breaking of one of the Cu–Q bonds to generate an active catalytic species.     

Preparation of (2,2-difluoroethenylidene)bis(tributylstannane) and arylation reaction: efficient approach to 1,1-diaryl-2,2-difluoroethenes

Reaction of 2,2-difluoro-1-tributylstannylethenyl p-toluenesulfonate (1) with bis(tributyltin) in the presence of 5 mol % Pd(PPh₃)₄ and 30 equiv LiBr in THF at reflux temperature for 7 h afforded (2,2-difluoroethenylidene)bis(tributylstannane) (2) in a 70% yield. Coupling reaction of 2 with aryl iodides in the presence of 5 mol % Pd(PPh₃)₄ and 5 mol % CuI in DMF at 80 °C for 3–4 h provided the coupled products 3 in 59–85% yields.     

DFT and ab initio calculations on the reaction between fluorine atoms and the fire suppressant, 2-H heptafluoropropane

Benchmark values for the reaction enthalpy (298 K) and the barrier height (0 K) of the reaction, CF₃CHFCF₃ + F → CF₃CFCF₃ + HF, have been calculated at state-of-the-art ab initio level to be −34.7 ± 1.0 and −0.9 ± 0.9 kcal/mole, respectively. The B3LYP, BH&HLYP, BB1K, MPW1K, MPWB1K and TPSS1KCIS functionals and the model method, the integrated molecular orbital + molecular orbital (IMOMO) method, have also been used to study this reaction.     

A time-dependent wave packet study of the H4 four-center reaction

A quantum model based on the time-dependent initial state selected wave packet approach was developed to study the four-center (4C) reaction, A₂ + B₂ → 2AB, and the competing collision induced dissociation (CID), A₂ + B₂ → A + B₂ + A, as applied to the H₂(v₁) + H₂(v₂) system important in combustion. A reduced three-dimensional model of the reaction with the atoms constrained to an isosceles trapezium and a realistic global potential energy surface of Aguado et al. [J. Chem. Phys. 101 (1994) 2742], following Hernández and Clary [J. Chem. Phys. 104 (1996) 8413], was used. A method to analyse the reaction flux for 4C and CID reaction probabilities is presented. The initial A₂ vibrational excitation is not only more efficient than translational energy in facilitating the 4C and CID processes, it also reduces the threshold energy. Both the 4C and CID processes exhibit similar threshold energy behavior. For low vibrational excitation in the A₂ diatom, the 4C process is dominant; as the A₂ diatom becomes highly excited the CID process becomes more important at low collision energies with B₂, but as the collision energy increases the 4C process is favored again.     

Halogenation of Lewis acid/base stabilised phosphanylboranes

The reaction pattern of the Lewis-acid/base stabilised phosphanylborane [(CO)₅W(H₂PBH₂ · NMe₃)] (1) with elemental halogens is comprehensively studied. The reaction with iodine and bromine leads to a selective halogenation at the tungstencarbonyl moiety under formation of [WX₂(CO)₄(H₂PBH₂ · NMe₃)] (X = I (2), Br (3)). Whereas 2 is a stable product the brominated compound 3 dimerises easily to [WBr₂(CO)₃(H₂PBH₂ · NMe₃)]₂ (4) under lost of CO. The CO elimination reaction of 3 is extensively studied. If 3 is reacted with [Et₄N][Br] the ionic compound [Et₄N][WBr₃(CO)₃(H₂PBH₂ · NMe₃)] (5) is formed. Otherwise, if 3 is combined with the donor ligand [H₂PBH₂ · NMe₃], the complex [WBr₂(CO)₃(H₂PBH₂ · NMe₃)₂] (6) is obtained. Compounds 2–6 are comprehensively characterised by X-ray diffraction analysis, NMR, and IR spectroscopy.     

Insertion of the p-complex structure of silylenoid H2SiLiF into X–H bonds (X = C,Si, N,P, O,S, and F)

The insertion reactions of the p-complex structure (A) of silylenoid H₂SiLiF into XH_n molecules (X = C, Si, N, P, O, S, and F; n = 1–4) have been studied by ab initio calculations at the G3(MP2) level. The results indicate that the insertion reactions of A into X–H bonds proceed via three reaction paths, I, II, and III, forming the same products, substituted silanes H₃SiXH_n − 1 with dissociation of LiF, respectively, and all insertion reactions are exothermic. All the seven X–H bonds can undergo insertion reactions with A via path I and II, but only four of them, C–H, Si–H, P–H, and S–H, undergo insertion reactions via path III. The following conclusions emerge from this work: (i) the X–H insertion reactions of A occur in a concerted manner via a three-membered ring transition state; (ii) for path I and II, the stabilization energies of the A–XH_n complexes decrease in the order HF > H₂O > H₂S > NH₃ > SiH₄ > CH₄; (iii) for path I and II, the greater the atomic number of heteroatom (X) in a given row, the easier the insertion reaction of XH_n hydrides and the larger the exothermicity, and for the second-row hydrides, the reaction barriers are lower than for the first-row hydrides; (iv) The barriers of path I are lowest in those of three pathways with the exception of A + SiH₄ system, which barrier of path III is lowest. Moreover, the present study demonstrates that both electronic and steric effects play major roles in the course of insertion reactions of A into X–H bonds.     

Synthesis of unsymmetrically disubstituted ethynes by the palladium/copper(I)-cocatalyzed sila-Sonogashira–Hagihara coupling reactions of alkynylsilanes with aryl iodides,bromides, and chlorides through a direct activation of a carbon–silicon bond

In this paper, we explore the copper/palladium-cocatalyzed cross-coupling reactions of 1-aryl-2-trimethylsilylethynes with aryl iodides, bromides, and chlorides as coupling partners, to furnish unsymmetrically disubstituted ethynes in moderate to excellent yields. Various aryl iodides were subjected to reaction under the optimized conditions with 5 mol % of Pd(PPh₃)₂ and 50 mol % of CuCl. The steric properties of the aryl iodide proved more influential to the outcome of the cross-coupling reaction than electronic factors. In addition, we succeeded in synthesizing unsymmetrical diarylethynes using two different aryl iodides in one-pot. Furthermore, under the same reaction conditions with 10 mol % of PdCl₂, 40 mol % of P(4-FC₆H₄)₃, and 50 mol % of CuCl as catalyst, we succeeded in synthesizing unsymmetrical diarylethynes from various aryl bromides. Finally, we explored reactions with aryl chlorides and duly discovered that unsymmetrical diarylethynes were obtainable in moderate to good yields when 10 mol % of Pd(OAc)₂, 10 mol % of (?)-DIOP, and 10 mol % of CuCl were used. These reactions proceed through a direct activation of a carbon–silicon bond in alkynylsilanes by CuCl to generate the corresponding alkynylcopper species via transmetalation from silicon to copper. Mechanistic investigations on the reaction of alkynylsilanes with aryl bromides confirmed that the trimethylsilyl bromide generated in situ retarded both transmetalation steps between CuCl and alkynylsilane, and between palladium(II) species formed by oxidative addition and alkynylcopper species.     

Novel electrocatalysts for generating oxygen from alkaline water electrolysis

We have obtained spinel-type Co₃O₄ and La-doped Co₃O₄ in the form of thin film on Ni, using microwave-assisted synthesis, which dramatically exhibit very low overpotentials for the oxygen evolution reaction (OER). Investigations have shown that at the apparent current density of 100 mA cm⁻² in 1 mol dm⁻³ KOH at 25 °C, the new electrodes, Co₃O₄ (oxide loading = 3.4 ± 0.3 mg cm⁻²) and La-doped Co₃O₄ (oxide loading = 2.8 ± 0.4 mg cm⁻²), produce overpotentials, 235 ± 7 and 224 ± 8 mV, respectively. Such low overpotentials for the OER, to our knowledge, have not been found on any mixed oxide electrode material reported in literature till today. Small La addition improved the BET surface area and porosity of the oxide catalyst powder and reduced the charge transfer resistance for the OER on the electrode made of oxide powder.     

Li0.93[Li0.21Co0.28Mn0.51]O2 nanoparticles for lithium battery cathode material made by cationic exchange from K-birnessite

Li_0.93[Li_0.21Co_0.28Mn _0.51]O₂ nanoparticles with an R-3m space group is hydrothermally prepared from Co_0.35Mn_0.65O₂ obtained from an ion-exchange reaction with K-birnessite K_0.32MnO₂ at 200 °C. Even at a hydrothermal reaction temperature of 150 °C, the spinel (Fd3m) phase is dominant, and a layered phase became dominant by combining an increase in the temperature to 200 °C with an increase in lithium concentration. The as-prepared cathode particle has plate-like hexagonal morphology with a size of 100 nm and thickness of 20 nm. The first discharge capacity of the cathode is 258 mAh/g with an irreversible capacity ratio of 22%, and the capacity retention after 30 cycles is 95% without developing a plateau at ∼3 V. Capacity retention of the cathode discharge is 84% at 4C rate (=1000 mA/g) and shows full capacity recovery when decreasing the C rate to 0.1 C.     

Li(4−x)/3Ti(5−2x)/3CrxO4 (0 ≤ x ≤ 0.9) spinels: New negatives for lithium batteries

Members of the spinel solid solution between Li_4/3Ti_5/3O₄ and LiCrTiO₄, i.e., Li_(4−x)/3Ti_(5−2x)/3Cr_xO₄ (0 ≤ x ≤ 0.9), have been investigated as possible negative electrodes for future lithium-ion batteries. Electrochemical behaviour have been studied over the potential range 1–3.5 V vs Li⁺/Li. Results are promising with anodic capacities between 129 and 163 mA h/g with a flat operating voltage at about 1.5 V, which is attributed to the pair Ti⁴⁺/Ti³⁺. The inclusion of Cr³⁺ in the spinel structure enhances the specific capacity. In-situ X-ray diffraction experiments confirm that the reaction proceeds in a topotactic manner.     

High-throughput investigation and characterization of strontium-phosphonatoethanesulfonates

Using the polyfunctional ligand 2-phosphonethanesulfonic acid (H₃L) a high-throughput (HT) study was started for the systematic investigation of the system SrCl₂/H₃L/NaOH/H₂O. The HT experiment comprising 48 individual reactions were performed to systematically investigate the influence of pH of the starting mixture as well as the molar ratio Sr²⁺:H₃L. Two new compounds SrH(O₃P–C₂H₄–SO₃) (1) and Sr₃(O₃P–C₂H₄–SO₃)₂(H₂O)₂ (2) were obtained and structurally characterized by single-crystal X-ray diffraction. The reaction products synthesized under hydrothermal conditions always contain traces of SrSO₄, which are due to the decomposition of small amounts of the ligand. While compound 2 could only be obtained under hydrothermal conditions, the synthesis of 1 could be accomplished under milder reaction conditions and a reaction scale-up could be performed. Compound 1 crystallizes in a monoclinic system with space group C2/c (no. 15), a = 534.73(11) pm, b = 1648.7(3) pm, c = 825.43(17) pm, β = 105.34(3)°, V = 701.8(2)–10⁶ pm³, Z = 4, R1 = 0.0268, and wR₂ = 0.0642 for I > 2σ(I). Compound 2 crystallizes in a triclinic system with space group P-1 (no. 2), a = 700.97(14) pm, b = 1008.5(2) pm, c = 1274.8(3) pm, α = 97.63(3)°, β = 92.03(3)°, γ = 92.03(3)°, V = 843.7(3)–10⁶ pm³, Z = 2, R1 = 0.0360, and wR₂ = 0.0896 for I > 2σ(I). In the structure of compound 1 the phosphorous and sulfur atoms cannot be distinguished due to identical crystallographic positions. Thus, an averaged structure was obtained which is built up by edge-sharing SrO₈ polyhedra that form infinite M–O–M chains. Compound 2 contains corner-, edge-, and face-sharing SrO₈ polyhedra which form inorganic M–O–M layers. These M–O–M chains (1) and layers (2) are connected to a three-dimensional network by the –CH₂CH₂– group of the ligand, respectively. Additional characterization by thermogravimetric analysis and IR-spectroscopy for compound 1 is also presented.     

Dual-signal anodic stripping voltammetric determination of trace arsenic(III) at a glassy carbon electrode modified with internal-electrolysis deposited gold nanoparticles

A glassy carbon electrode (GCE) modified with internal-electrolysis deposited gold nanoparticles (AuNPs_ied) was applied to sensitively and selectively detect As(III) by anodic stripping linear sweep voltammetry (ASLSV). The AuNPs_ied/GCE was prepared based on the redox replacement reaction between a supporting-electrolyte-free aqueous HAuCl₄ and a copper sheet in saturated KCl separated by a salt bridge. Under optimum conditions (0.5 M aqueous H₂SO₄, 300-s preconcentration at − 0.4 V), the ASLSV peak current for the As(0)–As(III) oxidation responded linearly to As(III) concentration from 0.02 to 3 μM with a limit of detection (LOD) of 0.9 nM (0.07 μg L^− 1) (S/N = 3), while that for the As(III)–As(V) oxidation was linear with As(III) concentration from 0.02 to 1 μM with a LOD of 4 nM (0.3 μg L^− 1) (S/N = 3). An appropriate high-scan-rate for ASLSV can enhance both the sensitivity and signal-to-noise ratio. This method was applied for analyses of As(III) in real water samples.     

Sc(OTf)3/TsOH: a highly efficient catalytic system for the synthesis of 2,6-dioxabicyclo[3,2,1]octane derivatives

A variety of aldehydes undergo a tandem acetalization and intramolecular Prins cyclization with pent-4-ene-1,2-diol in the presence of 5 mol % scandium triflate and 15 mol % p-toluenesulfonic acid (TsOH) in dichloroethane at 80 °C to produce the corresponding bicyclic ethers, that is, 2,6-dioxabicyclo[3,2,1]octane derivatives in good yields and with high selectivity. The salient features of this methodology are higher yields, lower catalyst loadings, and faster reaction times. The combination of Sc(OTf)₃ and TsOH (1:3) was found to be more effective than either Sc(OTf)₃ or TsOH alone.     

Effects of calcination and activation temperature on dry reforming catalysts

The effect of calcination temperatures on dry reforming catalysts supported on high surface area alumina Ni/γ-Al₂O₃ (SA-6175) was studied experimentally. In this study, the prepared catalyst was tested in a micro tubular reactor using temperature ranges of 500, 600, 700 and 800 °C at atmospheric pressure, using a total flow rate of 33 ml/min consisting of 3 ml/min of N₂, 15 ml/min of CO₂ and 15 ml/min of CH₄. The calcination was carried out in the range of 500–900 °C. The catalyst is activated inside the reactor at 500–800 °C using hydrogen gas. It was observed that calcination enhances catalyst activity which increases as calcination and reaction temperatures were increased. The highest conversion was obtained at 800 °C reaction temperature by using catalyst calcined at 900 °C and activation at 700 °C. The catalyst characterization conducted supported the observed experimental results.     

Copper and cadmium phosphonates based on 2-quinolinephosphonate

Hydrothermal reactions of 2-quinolinephosphonic acid (1) and CuSO₄ or CdSO₄ result in two new compounds with formula Cu(2-C₉H₆NPO₃) (2) and Cd(2-C₉H₆NPO₃)(H₂O) (3). Compound 2 has a layer structure in which dimers of edge-sharing {CuO₄N} square-pyramids are linked by {CPO₃} tetrahedra through corner sharing. Compound 3 shows a new type of layer structure where chains of corner sharing {CdO₅N} octahedra are connected by {CPO₃} tetrahedra into an inorganic layer. The quinoline groups fill in the inter-layer spaces in both cases. Crystal data for 1: monoclinic, space group P2₁/c, a = 10.270(2) Å, b = 13.566(3) Å, c = 6.9818(16) Å, β = 101.916(4)°, V = 951.8(4) Å³, Z = 4. For 2: monoclinic, space group P2₁/c, a = 13.976(3) Å, b = 7.9398(18) Å, c = 7.8687(18) Å, β = 101.150(5)°, V = 856.7(3) Å³, Z = 4. For 3: monoclinic, space group P2₁/c, a = 17.164(4) Å, b = 5.4870(12) Å, c = 10.850(2) Å, β = 101.557(4)°, V = 1001.1(4) Å³, Z = 4. The magnetic measurement on 2 reveals a dominant antiferromagnetic exchange coupling between the Cu(II) centers. A quasi-reversible electrochemical reaction is observed for complex 2 immobilized on the surface of GC electrode, corresponding to the redox couple Cu²⁺/Cu⁺. The fluorescent properties of 1–3 are also investigated.     

Low-temperature performance of LiFePO4/C cathode in a quaternary carbonate-based electrolyte

The low-temperature performance of LiFePO₄/C cathode in a quaternary carbonate-based electrolyte (1.0 M LiPF₆/EC+DMC+DEC+EMC (1:1:1:3, v/v)) was studied. The discharge capacities of the LiFePO₄/C cathode were about 134.5 mAh/g (20 °C), 114 mAh/g (0 °C), 90 mAh/g (−20 °C) and 69 mAh/g (−40 °C) using a 1C charge–discharge rate. Cyclic voltammetry measurements show obviously sluggish of the lithium insertion–extraction process of the LiFePO₄/C cathode as the operation temperature falls below −20 °C. Electrochemical impedance analyses demonstrate that the sluggish of charge-transfer reaction on the electrolyte/LiFePO₄/C interface and the decrease of lithium diffusion capability in the bulk LiFePO₄ was the main performance limiting factors at low-temperature.     

Radiotracer and analytical evidences proving the reduction of ClO4− ions at the cobalt/electrolyte solution interface

The occurrence of the reduction of ClO₄⁻ ions in the course of the dissolution (corrosion) of Co was indicated through the study of the adsorption of radio labelled (³⁶Cl) Cl⁻ ions. A detailed analytical study determining the Co²⁺ and Cl⁻ content of the solution phase furnished firm evidences that under suitable chosen experimental conditions the 4Co + ClO₄⁻ + 8H⁺=4Co²⁺ + Cl⁻ + 4H₂O reaction could be as important as the Co + 2H⁺=Co²⁺ + H₂ reaction considered in the literature as the only reaction path.     

Photocatalysis of 4-nitrophenol using zinc phthalocyanine complexes

Photodegradation of 4-nitrophenol (4-Np) in the presence of zinc tetrasulfophthalocyanine (ZnPcS₄), zinc octacarboxyphthalocyanine (ZnPc(COOH)₈) and a sulfonated ZnPc containing a mixture of differently sulfonated derivatives (ZnPcS_mix), as photocatalysts is reported. ZnPcS_mix is the most effective catalyst in terms of a high quantum yield for 4-Np degradation and the stability of the catalyst. However ZnPc(COOH)₈ degrades readily during the catalysis, but it has a higher quantum yield (Φ_4-Np) for 4-Np degradation than the rest of the complexes. The Φ_4-Np values were closely related to the singlet oxygen quantum yields Φ_Δ and hence aggregation. The rate constants for the reaction with 4-Np were k_r = 0.67 × 10⁶ mol⁻¹ dm³ s⁻¹ for ZnPcS_mix and 2.8 × 10⁸ mol⁻¹ dm³ s⁻¹ for ZnPc(COOH)₈.     

[MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety

A series of organometallic molybdenum/iron/sulfur clusters of the general formula [Cp¹MoFe₃S₄L_n]^m (Cp¹ = η⁵-C₅Me₅; L = S^tBu, SPh, Cl, I, n = 3, m = 1−; L_n = I₂(P^tBu₃), m = 0; L = 2,6-diisopropylphenylisocyanide (ArNC), n = 7, m = 1+) have been synthesized. A cubane cluster (PPh₄)[Cp¹MoFe₃S₄(S^tBu)₃] (2) was isolated from a self-assembly reaction of Cp¹Mo(S^tBu)₃ (1), FeCl₃, LiS^tBu, and S₈ followed by cation exchange with PPh₄Br in CH₃CN, while an analogous cluster (PPh₄)[Cp¹MoFe₃S₄(SPh)₃] (3) was obtained from the Cp¹MoCl₄/FeCl₃/LiSPh/PPh₄Br reaction system or from a ligand substitution reaction of 2 with PhSH. Treatment of 2 with benzoyl chloride gave rise to (PPh₄)[Cp¹MoFe₃S₄Cl₃] (4), which was in turn converted to (PPh₄)[Cp¹MoFe₃S₄I₃] (5) by the reaction with NaI. A neutral cubane cluster Cp¹MoFe₃S₄I₂(P^tBu₃) (6) was generated upon treating 5 with P^tBu₃. Although reduction of 4 by cobaltocene under the presence of ArNC resulted in a disproportionation of the cubane core to give Fe₄S₄(ArNC)₉Cl (7), a similar reduction reaction of 5 produced [Cp¹MoFe₃S₄(ArNC)₇]I (8), where the MoFe₃S₄ core was retained. The crystal structures of 4–6, and 8 were determined by the X-ray analysis.