Anhydrous SnCl2 Research Articles

Experimental conditions for room temperature ferromagnetism in Fe-doped SnO2 via mechanochemical milling and thermal treatment

Identifying optimal experimental conditions, preferably through a simple and cost-effective method, for the fabrication of oxide-diluted magnetic semiconductors, such as Fe-doped SnO2, holds great significance in the quest for spintronic materials operating at room temperature (RT). While mechanochemical milling is a well-established technique meeting these requirements, its numerous milling variables necessitate careful consideration of restricted experimental conditions. In this study, we present some experimental mechanochemical milling conditions to prepare impurity-free iron-doped tin dioxide nanoparticles exhibiting RT ferromagnetic signal. To achieve this, we investigated the effects of milling time, the choice of the starting Sn reactant, and iron concentration on the purity of Sn1−xFexO2 (x = 0, 0.03, and 0.05) nanopowders obtained through mechanochemical milling followed by thermal treatment. Characterization through XRD, XANES, and EXAFS at the Fe K-edge, RT Raman spectroscopy, 119Sn and 57Fe Mössbauer spectroscopies, and magnetic measurements was conducted. Among the experimental techniques, micro-Raman spectroscopy proved the most effective in detecting the formation of hematite as an impurity phase. Our results indicate that extending the milling time to 12 h, as opposed to 3 h, employing anhydrous SnCl2, instead of SnCl2·2H2O and using the low iron concentration of x = 0.03, results in proper conditions for producing impurity-free samples with a robust RT ferromagnetic signal. The oxidation states for iron and tin ions were determined to be 3+ and 4+, respectively, with both occupying octahedral sites, suggesting iron’s replacement of tin. Our findings propose that both the bound magnetic polaron and RKKY models offer potential explanations for the origin of the ferromagnetic signal observed at room temperature in Sn0.97Fe0.03O2 sample milled for 12 h.

Evaluation of natural staining on Wistar rat EMI region using different metal salts

Background: The natural staining of cells has recently become a growing research topic. Roselle (Hibiscus sabdariffa) chemical structure has two main components that contain more chromophore groups. Objectives: The aim of this study is to dye cells and elements in two important parts of the Wistar rat uterus with roselle extract containing dense flavonoids and metal salts. Methods: In this study, dried and clean Hibiscus sabdariffa obtained from the local market was used for histological staining of uterine layers (EMI region) in Wistar rat tissue. Different cell structures and their different pathological evaluations are made in the EMI region. In order to more reach different cells, solutions of one percent anhydrous SnCl2 (tin chloride), 1% FeSO4.5H2O (ferrous sulfate), and 1% KAlSO4.12H2O (alum) metal salts in distilled water were used in this study. Results: In staining with roselle extracts containing alum and iron sulfate, tissue red-colored endometrial cell staining, and bluepurple stained inflammatory cells were observed in staining with roselle extract containing 1% SnCl2. Conclusions: Cytoplasmic and nuclear staining intensity, bluing, and clarity were better when SnCl2 was used as the bluing or bruising agent. A purple chelates and coordinate covalent bonding between Flavonoids in the roselle structure and the protein structures in the cell was formed by tin metal in SnCl2 solution. In fact, that there are blue-purple-stained regions in different shades in the cell structure suggests that flavonoids stain different uterine cells thanks to SnCl2. This situation may help to evaluate different and complex pathological findings in the uterus.

Homogeneous Lewis and Brønsted acids as catalysts for β-pinene oxide rearrangement to prepare myrtenol and myrtanal

Myrtenol and myrtanal find their utilization as fine chemicals or intermediates for the synthesis of food additive myrtanol. β-Pinene oxide rearrangement was studied using homogeneous Lewis and Brønsted acids as catalysts for the production of these compounds. The composition of reaction products depended on the type of active sites. Lewis active sites favoured the formation of myrtanal while in presence of Brønsted active sites undesirable perillyl aldehyde and perillyl alcohol were formed to a high extent. Optimal reaction conditions for myrtenol and myrtanal preparation were found. With 5 mol.% of anhydrous SnCl2 as Lewis acid catalysts and 1,4-dioxane as the solvent β-pinene oxide achieved total conversion with 95% selectivity to desired products.

P-Cymene Ruthenium Halide Complexes with a Heterocyclic Carbene

The reaction of (p-cymene)Ru(Me2Im)Cl2 with excess Me2ImCO2 in acetonitrile in the presence of NH4PF6 afforded the amino complex [(p-cymene)Ru(Me2Im)(NH3)Cl]PF6. The reaction of (p‑cymene)Ru(Me2Im)Cl2 with excess anhydrous SnCl2 gave the complex (p-cy-mene)-Ru(Me2Im)Cl(SnCl3), whereas treatment of dimeric iodide complex [(p-cymene)RuI2]2 with Me2ImCO2 in acetonitrile gave the ionic compound [Me2ImH][(p-cymene)RuI3]. CIF files: CCDC nos. 1841649 (I), 1841650 (II), 1841648 (III).

Stannyl Complexes of Rhodium and Iridium: Preparation of Mono‐ and Bis(trihydridestannyl) Derivatives

AbstractMono‐ and bis(trichlorostannyl) complexes [MCl(SnCl3)(η5‐C5Me5){P(OR)3}] (1, 2) and [M(SnCl3)2(η5‐C5Me5){P(OR)3}] (3, 4) (M = Rh, Ir; R = Me, Et) were prepared by allowing chloro compounds MCl2(η5‐C5Me5)[P(OR)3] to react with anhydrous SnCl2 in refluxing 1,2‐dichloroethane. Treatment of trichlorostannyl complexes of iridium 2 and 4 with NaBH4 in ethanol afforded hydride‐trihydridestannyl derivatives [IrH(SnH3)(η5‐C5Me5){P(OR)3}] (5) and bis(trihydridestannyl) [Ir(SnH3)2(η5‐C5Me5){P(OR)3}] (6), the reaction of which with methylpropiolate HC≡CCOOMe led to trivinylstannyl derivatives [IrH{Sn[C(COOMe)=CH2]3}(η5‐C5Me5){P(OMe)3}] (7 a) and [Ir{Sn[CH=C(H)COOMe]3}2(η5‐C5Me5){P(OMe)3}] (8 a). The complexes were characterised spectroscopically (IR and 1H, 31P, 13C, 119Sn NMR) and by X‐ray crystal structure determination of [Ir(SnCl3)2(η5‐C5Me5){P(OMe)3}] (4 a).

Cation-Triggered Stannate(II)/Stannylenoid/Stannylene Conversion.

The reaction of dipotassio-tetrasilan-1,4-diide (4) with anhydrous SnCl2 at low temperature results in the formation of a five-membered cyclic potassio chlorostannate(II) ([(18-C-6)K](1)). By careful cation exchange reactions, it was transformed into the sodium chlorostannylenoid 2 (by using Na2 [B12 Cl12 ]) or into the non-stabilized cyclic bissilylstannylene 3 (through applying Li[Al(OC(CF3 )3 )4 ]). The increasing Lewis basicity of the bissilylstannylene 3 was analyzed by combined methods of DFT calculations and NMR spectroscopy and substantiated by the synthesis of the corresponding iron carbonyl complexes 7 and 8 from the chlorostannate 1 and the stannylene 3, respectively.

One‐pot Method for Reduction of Pyrazolo[5,1‐c][1,2,4]Triazine‐7‐diazonium Tetrafluoroborate to 7‐Hydrazinyl Derivatives

New convenient one‐pot method for reduction of hetarenediazonim tetrafluoroborates to the hetarylhydrazine derivatives was developed. Interaction of 8‐carboxyethyl‐3‐(tert‐butyl)‐4‐oxo‐4,6‐dihydropyrazolo[5,1‐c][1,2,4]triazine‐7‐diazonium tetrafluoroborate with anhydrous SnCl2 in anhydrous CF3CO2H, and further sequence of one‐pot operations led to formation of various derivatives of the unstable ethyl 3‐(tert‐butyl)‐7‐hydrazinyl‐4‐oxo‐4,6‐dihydropyrazolo[5,1‐c][1,2,4]triazine‐8‐carboxylate (hydrochloride, hydrazides, hydrazones, and pyrazoles), which were isolated in high yields. The anhydrous conditions were first used with SnCl2 and allowed to exclude hydrolysis of the ester group and formation of the by‐products.

SnCl2/EtOH-Mediated Synthesis of Novel 4-Ethoxy- and 4-Chloroindazoles Bearing Sulfonamide Moieties

The treatment of N-alkyl-5-nitroindazole with stannous chloride in ethanol, aftercoupling of the obtained amines with arylsulfonyl chloride in pyridine, gave the new 4-ethoxy- and 4-chloroindazoles bearing sulfonamide in moderate to good yields. Chlorination and ethoxylation of indazole were observed during the reduction of the nitro group with anhydrous SnCl2 in ethanol. The influence of the N-alkylation in N-1 and N-2 position of 5-nitroindazole on the reduction was investigated. The presence ofethoxy group and chlorine atom at position C-4 of indazole was confirmed by x-ray diffraction analysis of compounds 7a and 8a.

Heterogeneous catalytic synthesis of poly(butylene succinate) by attapulgite‐supported Sn catalyst

ABSTRACTAn attapulgite‐supported Sn catalyst (Sn‐palgorskite) was successfully prepared by ion‐exchange co‐impregnation method. The catalytic effect of Sn‐attapulgite on the melt polycondensation reaction of poly(butylene succinate) (PBS) was examined by comparing with that of anhydrous SnCl2 and a blank experiment. The structures and properties of the PBS products synthesized with the three catalytic systems were characterized by means of Fourier transform‐infrared spectra (FT‐IR), viscosity measurements, wide angle X‐ray diffraction (WARD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Meanwhile, the acidolysis degradation behaviors of the PBS samples were also studied. It was found that the intrinsic viscosities and the number‐average molecular weights of the PBS were remarkably increased under the catalysis of Sn‐attapulgite, further leading to an increase in the decomposition temperature, the crystallization temperature, and the viscous flow activation energy, while a decrease in the melting temperature, the relative degree of crystallinity, and the rate of degradation. Additionally, no significant differences were observed in the crystal structures of all the samples, regardless of the reaction system with or without catalyst. The experiment results confirmed that Sn‐attapulgite was an effective heterogeneous catalyst for the synthesis of PBS, and the recycled Sn‐attapulgite still exhibited higher activity than anhydrous SnCl2 under identical reaction conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41729.

Ionic liquid-assisted sonochemical synthesis of SnS nanostructures

SnS nanoparticles have been successfully synthesized by the ionic liquid-assisted sonochemical method (ILASM). The starting reagents were anhydrous SnCl2, thioacetamide, dissolved in ethanol and ionic liquid (IL)1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) mixtures. Our experiments showed that IL plays an important role in the morphology of SnS. A 1:1 ethanol:IL mixture was found to yield the more interesting features. The lower concentration of Sn (II) in solution favored the presence of nanoplatelets. An increase in ultrasonic time favored crystalline degree and size as well. Also, the effect of additives as 3-mercaptopropionic acid, diethanolamine, ethylene glycol, and trioctyl phosphine oxide is reported. X-ray diffraction (XRD) and ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis-DRS) were used to characterize the obtained products.

Deep extractive and oxidative desulfurization of dibenzothiophene with C5H9NO·SnCl2 coordinated ionic liquid

A new C5H9NO·SnCl2 coordinated ionic liquid (IL) was prepared by reacting N-methyl-pyrrolidone with anhydrous SnCl2. Desulfurization of dibenzothiophene (DBT) via extraction and oxidation with C5H9NO·SnCl2 IL as extractant, H2O2 and equal mol of CH3COOH as oxidants was investigated. The Nernst partition coefficients kN of C5H9NO·SnCl2 IL for the DBT in n-octane was above 5.0, showing its excellent extraction ability. During the oxidative desulfurization process, the optimal molar ratio of H2O2/DBT was six. Sulfur removal of DBT in n-octane was 94.8% in 30min at 30°C under the conditions of H2O2/DBT molar ratio of six and V (IL):V (oil)=1:3. Moreover, the sulfur removal increased with increasing temperature because of the high reaction rate constant, low viscosity, and high solubility of dibenzothiophene-sulfone in the IL. The kinetics of oxidative desulfurization of DBT was also investigated, and the apparent activation energy was found to be 32.5kJ/mol. The IL could be recycled six times without a significant decrease in activity.

Studies on the Reduction of the Nitro Group in 4-Nitroindazoles by Anhydrous SnCl2 in Different Alcohols

The synthesis of new 7-alkoxy-4-amino-protected indazole and 4-amino-protected indazole derivatives by the reduction of the nitro group of 4-nitroindazoles using anhydrous stannous chloride in different alcohols is described.

Alkylation and Reduction of N-Alkyl-4-nitroindazoles with Anhydrous SnCl2 in Ethanol: Synthesis of Novel 7-Ethoxy-N-alkylindazole Derivatives

Alkylation and Reduction of N-Alkyl-4-nitroindazoles with Anhydrous SnCl2 in Ethanol: Synthesis of Novel 7-Ethoxy-N-alkylindazole Derivatives

Search for the stannous ion in a chloride/fluoride matrix: cases of Ba1−x Sn x Cl1+y F1−y and of Ba2SnCl6

With the exception of anhydrous SnCl2, in divalent tin fluorides and chlorides, tin(II) is always covalent bonded, i.e. its valence orbitals are hybridized and the tin lone pair is located in one of the hybrid orbitals. This lone pair is highly stereoactive and generates a large efg, resulting in a large quadrupole splitting. A doubly disordered Ba1−x Sn x Cl1+y F1−y solid solution has been prepared and found to contain either ionic tin(II) (Sn2+ ions) or a mixture of ionic and covalent tin(II), depending on x, y and the method of preparation. The ionic tin(II) spectrum in Ba1−x Sn x Cl1+y F1−y gives a Mossbauer single line that is broadened by the lattice efg, like in SnCl2. Now, Sn2+ has been found to be present in an undistorted octahedral coordination in a newly isolated compound, Ba2SnCl6. It should be the first example of Sn2+ that is fully ionic and has a perfectly spherical lone pair.

Kinetics of Catalytic Isomerization of Quadricyclane to Norbornadiene Using Near Infrared Absorption Spectroscopy: Conversion Rate and Diffusion Motion in Heterogeneous Reaction

By use of Fourier transform near-infrared (NIR) absorption spectroscopy and the aid of a kinetic model, we have investigated the conversion of quadricyclane to norbornadiene catalyzed by anhydrous CuSO4 and SnCl2 in chloroform. The reaction mixture is not agitated so as to avoid the effect of sample heterogeneity. The NIR absorption spectra are acquired, at a position ∼2 mm above the catalyst surface, at 30-s intervals during 4 h. The concentrations of quadricyclane and norbornadiene are determined with the analysis of partial least squares. The isomerization of quadricyclane, as numerically solved from the model, is expected to describe its behavior more accurately in the catalytic system than that obtained previously. In addition to the isomerization rate, the kinetic model takes into account the contribution of diffusion. The diffusion coefficients of quadricyclane can be determined to be 3.8 × 10-5 cm2 s-1 in chloroform and 1.14 × 10-5 and 2.85 × 10-6 cm2 s-1 inside the CuSO4 and SnCl2 stacks, respectively. Diffusion is slowed inside the solid stacks, and thus the molecular mechanism cannot be suitable for this system. Given the diffusion coefficients, the pseudo-first-order depletion rate constants are evaluated to be (3.7 ± 0.1) × 10-3 and (3.8 ± 0.1) × 10-3 s-1 for CuSO4 and SnCl2, respectively. The corresponding second-order rate constants are determined to be (1.3 ± 0.2) × 10-5 and (2.0 ± 0.1) × 10-6 s-1 A-1 by considering the density and the size of the catalyst particles; A denotes the total catalyst surface area per unit effective volume of solvent. The rate constant with the CuSO4 catalyst is consistent with others obtained in a continuously stirred mixture. In the surface-mediated reaction, the catalytic isomerization is subject to one-site coordination (1:1 complex) between the reactant and the catalyst. Nevertheless, a two-site coordinated reaction cannot be excluded unless the interstitial size dependence of the depletion rate is known.

Electrodeposited SnS thin films from aqueous solution

Considerable efforts have been made in recent years in the search for low-cost materials for solar energy conversion. Among the materials of great interest are polycrystalline metal chalcogenides. These can be synthesized by means of low-temperature chemical precipitation or vapour deposition techniques, as described in previous works [1, 2]. The materials may also be electrosynthesized, either cathodically [3‐5] or anodically [6‐8] from an aqueous or nonaqueous medium. Electrochemical methods, especially those performed in an aqueous medium, have recently received enormous attention due to their simplicity and cost effectiveness [9‐15]. In addition, they have the advantages of being low temperature processes, with low material wastage and with the possibility of using lower grade materials. This method has been extensively applied in the preparation of CdS and CdSe thin films. We report here the possibility of cathodic electrodeposition of another promising compound, tin sulphide (SnS), from aqueous solution. The electrodeposition was carried out on either titanium or an indium-doped tin oxide (ITO) glass substrate in a standard three-electrode cell. A saturated calomel electrode (SCE) or sometimes an Ag AgCl electrode was used as the reference electrode, while platelet or spiral Pt (99.9%) was used as the counter electrode. The deposition potential was controlled by an EG&G Princeton Applied Research (PAR) Versastat driven by model 270 Electrochemical Analysis System software. The substrate was polished and chemically and ultrasonically cleaned before being used. The electrodeposition bath was prepared from anhydrous SnCl2, sodium thiosulphate (Na2S2O3) and disodium ethylenediaminetetra-acetic acid (EDTA) salts using N2purged purified water from a Milli-Q water purification system. The resultant solution was acidified to a pH of about 1.5. The solution was continuously deaerated with N2 during electrodeposition. Prior to electrodeposition, cyclic voltammetry was run in order to determine the viable potential and to elucidate the electrochemical processes at the

A SYNTHESIS AND STRUCTURE OF A WATER-SOLUBLE TETRAPYRIDYLPORPHYRINATO TIN(IV) CHLORIDE

Abstract The water-soluble octahedral tin(IV) porphyrin complex, SnCl2tpyp, was synthesized via reaction of H2tpyp with anhydrous SnCl2. The crystal structure of this complex has been determined at room temperature. The tin(IV) atom is coordinated by four nitrogen atoms in a square-planar fashion with an average Sn-Np bond distance of 2.081(9)A, and the coordination sphere is completed by two axial chloro ligands with an average Sn-Cl bond distance of 2.435(5)A, Cl-Sn-Cl = 180.0 (1)°. Crystal data: a = 12.385(12), b = 26.88(2), c = 14.882(9)A, β = 94.16 (7)°, monoclinic, space group C2/c, V = 4941A3, Z = 4, C46H48Cl2N8O6Sn, 2687 observed data, R = 0.085.

Eleven-vertex polyhedral stannadicarbaborane chemistry. ‘naked tin’{closo-1,2,3-SnC2B8}-cluster compounds

Reaction of anhydrous SnCl2 with the nido ten-vertex anions [6,9-C2B8H10]2–, [6-Me-6,9-C2B8H9]2–, [6-Ph-6,9-C2B8H9]2– or [6,9-Me2-6,9-C2B8H8]2– in tetrahydrofuran solution results in the formation of [closo-1,2,3-SnC2B8H10](59%), [2-Me-closo-1,2,3-SnC2B8H9](34%), [2-Ph-closo-1,2,3-SnC2B8H9](21%) or [2,3-Me2-closo-1,2,3-SnC2B8H8](10%) respectively as volatile white solids. Their NMR properties suggest that the compounds are best regarded as true closo species analogous to closo-2,3-C2B9H11.

π‐Complexes of p‐block elements: (η6‐Mesitylene)tin(II) chloride tetrachloroaluminate(III), a coordination polymer

Abstract(η6‐1,3,5‐Trimethylbenzene)tin(II) chloride tetrachloroaluminate(III), (η6‐1,3,5‐C6H3Me3)SnCl (AlCl4), has been obtained from the reaction of anhydrous SnCl2 and AlCl3 in the molar ratio 1 : 2 in excess mesitylene as a solvent. The compound crystallizes in monoclinic needles, space group P21/n, containing a coordination polymer with planar four‐membered rings Sn‐Cl‐Sn‐Cl as the fundamental structural units. Each tin(II) atom of these rings is η6‐bonded to a mesitylene ring, with the metal approximately centered over the aromatic hydrocarbon at a distance of 2.71 Å. Each of the tin(II) atoms is further connected to two tetrachloroaluminate counter ions, one of these monodentate and one bidentate. Through this mono/bidentate contacts a one‐dimensional coordination polymer is generated with crystallographic centers of inversion in the middle of the Sn(Cl)2Sn and Sn(AlCl4)2Sn rings. The structure is similar to that of the analogous benzene complex, but not identical owing to a different connectivity pattern. Also, the arene‐Sn(II) distance is much shorter in the mesitylene complex (2.71 Å) than in the benzene complex (2.90 Å), indicating that the trimethylbenzene molecule is a much better donor than benzene.

π-Complexes of p-Block Elements: [(η6-C6Me6)Sn(AlCl4)2]2•3 C6H6 — a Dimeric Coordination Compound of Hexamethylbenzene with Sn(AlCl4)2

Dimeric (η6-hexamethylbenzene)tin(II)bis(tetrachloroaluminate), [(η6-C6Me6)Sn(AlCl4)2]2, has been obtained from the reaction of anhydrous SnCl2, AlCl3, and hexamethylbenzene in the molar ratio of 1:2:1 in benzene as a solvent. The complex, which crystallizes in the triclinic space group PĪ, contains a folded eight-membered ring Al2Sn2Cl4 2+, with the two tin(II) centers linked by two bidentate bridging AICl4- counterions. Each tin(II) atom is η6-bonded to a hexamethylbenzene ring at a distance of 2.45 Å — the shortest Sn-to-arene distance ever found in the tin(II)/arene system. Each tin(II) atom is further connected to another AICl4- anion, also acting as a bidentate ligand, but without contacts to other tin(II) centers. The three crystal benzene molecules show no specific metal contacts.