Selective solution-phase synthesis of BiOCl, BiVO4 and δ-Bi2O3 nanocrystals in the reaction system of BiCl3-NH4VO3-NaOH

In this study, we demonstrate a straightforward solution-phase method for the selective synthesis of BiOCl, BiVO₄ and δ-Bi₂O₃ nanocrystals by simply manipulating the reaction temperature and the BiCl₃-to-NaOH mole ratio in the reaction system of BiCl₃-NH₄VO₃-NaOH. The experimental results revealed that BiOCl, as the sole product, was prepared when designating the reaction temperature ranging from room temperature to 100 °C, regardless of the BiCl₃-to-NaOH mole ratio; on the other hand, BiOCl, BiVO₄, and δ-Bi₂O₃ nanocrystals could be selectively prepared at 140-180 °C, depending on the BiCl₃-to-NaOH mole ratio in solution. Significantly, we first report on fabricating δ-Bi₂O₃ sample, the high-temperature cubic phase commonly stabilized at 730-824 °C, at the low reaction temperature of 140-180 °C under solution-phase synthetic conditions. In addition, the δ-Bi₂O₃ sample exhibits strong emission at room temperature.     

Controlled synthesis of bismuth oxo nanoscale crystals (BiOCl, Bi12O17Cl2, α-Bi2O3, and (BiO)2CO3) by solution-phase methods

We present the controlled solution-phase synthesis of several sheet- or rod-like bismuth oxides, BiOCl, Bi₁₂O₁₇Cl₂, α-Bi₂O₃ and (BiO)₂CO₃, by adjusting growth parameters such as reaction temperature, mole ratios of reactants, and the base used. BiOCl, Bi₁₂O₁₇Cl₂, and α-Bi₂O₃ could be prepared from BiCl₃ and NaOH, whereas (BiO)₂CO₃ was prepared from BiCl₃ and urea. BiOCl and Bi₁₂O₁₇Cl₂ could also be prepared from BiCl₃ and ammonia. The α-Bi₂O₃ sample exhibited strong emission at room temperature.     

Polymer chlorobismuthate complex catena-{((Me,Me)Bpe)[BiCl5]} n : Synthesis and crystal structure

The reaction of BiCl₃ and N,N-dimethyl-1,2-bis(pyridyl)ethane chloride (Me,Me-Bpe) in 2 M HCl affords a polymer chlorobismuthate complex {((Me,Me)Bpe)[BiCl₅]} _n (I). The structure of complex I is determined by X-ray diffraction analysis (CIF file CCDC 1058842). The anionic moiety of the complex is presented by a 1D coordination polymer ([BiCl₅]^2n–) _n consisting of octahedral blocks {Cl₆} linked by µ₂- bridging chloride ligands into infinite zigzag chains.     

Bismuth Complexes in Phenylazomethine Dendrimers: Controllable Luminescence and Emission in the Solid State

Dendritic phosphors were obtained by the stepwise integration of BiCl₃ in phenylazomethine dendrimers. The bismuth‐coordinated phenylazomethines displayed photoluminescence at 500–800 nm, and the intensity could be tuned by changing the stoichiometry of BiCl₃ and the dendrimer. This phosphor did not show serious luminescence quenching even though the local concentration of BiCl₃ in the dendrimer was as high as 20 M , and luminescence was also observed in the solid state. The absorption and emission properties could be reversibly switched by addition of a Lewis base or under electrochemical redox control, which induced the reversible complexation of BiCl₃ in the dendrimer.     

BiCl3 promoted aza-Prins type cyclization: a rapid and efficient synthesis of 2,4-disubstituted piperidines

Several N-protected homoallyl amines and epoxides were subjected to an aza-Prins cyclization. A rapid and efficient BiCl₃ promoted stereoselective synthesis of trans-2,4-disubstituted piperidine derivatives was achieved.     

CF bond activation in the reaction of BiCl3 with sodium 2,4,6-tris(trifluoromethyl)phenoxide

BiCl₃ reacts with sodium 2,4,6-tris(trifluoromethyl)phenoxide (NaOR_4f) in ether solution to produce an unusual condensation product in which three OR_f functions have been coupled with the elimination of three fluorine atoms. The product is R_fOC₆H₂(CF₃)₂C(O)OR_f, which has been characterized spectroscopically and by X-ray crystallography (triclinic space group P 1; a = 8.958(1), b = 12.652(2), c = 13.722(2)Å, α = 89.596(8)°, β = 75.92(1)°, γ = 71.412(7)°, V = 1425.6(3)ų, Z = 2). Bi(OR_f)₃ is believed to be an intermediate in this process. The carbonfluorine bond activation is not observed in the absence of BiCl₃.     

A Role of the Plating Regime in the Deposition of Bismuth Films onto a Carbon Paste Electrode. Microscopic Study

A microscopic study is presented based on observations of bismuth films deposited from various plating solutions and under different experimental conditions onto the carbon paste surface. Electrolytic plating of bismuth films was performed either as simulation of preconcentration in‐situ from a 0.2 M acetate buffer containing 5×10^?5 M Bi³⁺ (pH 4.25), or as external deposition from various plating solutions: 0.1 M acetate buffer with 5×10^?4 M Bi³⁺ (pH 4.50), 0.5 M HCl with either 0.001 M BiCl₃ or 0.005 M BiCl₃ , 0.5 M HCl+0.5 M KBr+0.005 M BiCl₃ , and 0.5 M HCl+0.5 M KI+0.005 M BiCl₃ (all pH≈0.5). Scanning electron microscopic images of the bismuth films showed a considerable variability in structure and compactness of the deposited layer in dependence on experimental conditions chosen such as the concentration of Bi(III) species, the total acidity of plating media, the stability of complexes of Bi(III) with halogenide anions or the deposition potential applied.     

Crystalline and Glassy Phases in the Ternary System Tl/Bi/Cl: Synthesis and Crystal Structures of the Thallium(I) Chloridobismutates(III) Tl3BiCl6 and TlBi2Cl7

Slow cooling of melts composed of TlCl and BiCl₃ allows for the isolation of the compounds Tl₃BiCl₆ ( 1 ) and TlBi₂Cl₇ ( 2 ). Compound 1 is formed by sublimation at 480 °C from the black melt of 3 TlCl + 1 BiCl₃ as colourless crystals. The crystal structure determination (tetragonal, P4₂/m) consists of nearly regular octahedral [BiCl₆]^3– anions and two independent Tl⁺ cations, which have coordination number 8 in form of a slightly distorted cube and 10 in form of an Edshamar polyhedron, respectively. The structure is not isotypic with the recently reported naturally occurring form of Tl₃BiCl₆, the mineral steropesite. Compound 2 is obtained from a dark red melt of composition TlCl + 2 BiCl₃. On rapid cooling, this melt solidifies to a metastable dark red glass which at ambient temperature crystallises to a light amber crystalline powder within some weeks. The structure of 2 was determined by powder diffraction (triclinic, P\bar{1} ). A distinct lone pair effect is present causing an irregular coordination on the two independent bismuth atoms. Taking Bi–Cl bonds up to 3.5 Å into account, both bismuth atoms gain coordination number seven. ²⁰³Tl and ²⁰⁵Tl solid state NMR and XANES spectra on the Bi and Tl‐L_III edges of both glassy and crystalline TlBi₂Cl₇ show that a close structural similarity exists between both forms. In contrast, the Raman spectra show distinct differences in the bands of the Bi–Cl vibrations region.     

Spectra and structure for Bi0-BiCl3-Li,K/Cl

Raman-scattering, electronic-absorption, and ESR spectra have been used to determine the states of bismuth and the structures of the compounds formed in molten chloride systems; it is found that BiCl₄ ^– with T_d symmetry are formed in BiCl₃-Li, K/Cl_eu melts, while a Bi⁰-BiCl₃-Li, K/Cl_eu melt produces the BiCl₄ ^– BiCl₃ + Cl^–; BiCl₃ + Bi⁰ Bi₂Cl₃ equilibria with the formation of Cl^– the quasitetrahedral ion in the second stage, which has a metal-bond and a single unpaired electron.Institute for General and Inorganic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 3, pp. 311–315, May–June, 1991. Original article submitted September 12, 1988.     

NH<Subscript>3</Subscript>(CH<Subscript>2</Subscript>)<Subscript>5</Subscript>NH<Subscript>3</Subscript>BiCl<Subscript>5</Subscript>: an efficient and recyclable catalyst for the synthesis of benzoxazole,benzimidazole and benzothiazole heterocycles

In this work, the condensation of aromatic aldehydes with different two-substituted aniline catalyzed by NH₃(CH₂)₅NH₃BiCl₅ as heterogeneous and recyclable catalyst was reported. It was demonstrated that NH₃(CH₂)₅NH₃BiCl₅ can act as an efficient and active catalyst and is reusable for six runs without a significant loss of their catalytic activity. Simple preparation of the catalyst, high catalytic activity and good reusability are noteworthy advantages of this catalytic system in the synthesis of benzoxazole, benzimidazole and benzothiazole heterocycles at room temperature under solvent-free conditions.     

Untersuchungen zum System Bi2O3/BiCl3

Investigation on the System Bi₂O₃/BiCl₃ The temperature functions of decomposition pressures of the ternary compounds on the quasibinary line Bi₂O₃/BiCl₃ were determined by total pressure measurements and mass spectroscopy. The barogram of the system was constructed and the melting diagram precised. The enthalpies of formation and the standard entropies of the solid phases were derived from the decomposition functions: (Values see Inhaltsübersicht).     

Simple entry to new 2-alkyl-1,2,3,4-tetrahydroquinoline and 2,3-dialkylquinoline derivatives using BiCl3-catalyzed three component reactions of anilines and aliphatic aldehydes in the presence (or lack) of N-vinyl amides

A general protocol for the simple and efficient synthesis of 2-alkyl-1,2,3,4-tetrahydroquinolines and 2,3-dialkylquinolines was reported. Synthetic protocol describes the one-pot preparation of these tetrahydroquinoline and quinoline products using the same reagents (aliphatic aldehydes and anilines) in the BiCl₃-catalyzed multicomponent condensation process where the third component, N-vinyl amide is present.     

The directional polymeric chain of [(BiCl<Subscript>5</Subscript>)<Superscript>2−</Superscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> in 2,2′-Bi(2-1H-imidazolium) pentachlorobismuthate dihydrate

The title compound, (C₆H₆N₄)(BiCl₅) · 2H₂O, is built up by 2,2′-bi(2-1H-imidazolium) dications and (BiCl₅)²⁻ anions. Distorted BiCl₆ octahedra are joined with each other alternatively to form [(BiCl₅)²⁻] _n polymeric chains, where the bridging chlorine atoms are shared by two octahedra. The lone pair at the Bi atom shows obviously stereochemical activity, leading to distortion of the BiCl₆ octahedra and formation of the chain directionality. In solid state, the chains are stabilized by O-H···Cl and C-H···Cl hydrogen bonds. The article was submitted by the authors in English.     

Bismuth(III) salts mediated regioselective ring opening of epoxides: an easy route to halohydrins and β-hydroxy nitrates

The ring opening of various epoxides was achieved under mild conditions using bismuth(III) salts. Halohydrins and β-hydroxy nitrates were efficiently obtained from the corresponding 5α,6α-, 2α,3α-, and 5β,6β-epoxysteroid using BiCl₃, BiBr₃ or Bi(NO₃)₃·5H₂O. Considerations about the probable reaction mechanism are provided. 2D homo- and heteronuclear correlation NMR spectroscopic techniques were used to unequivocally demonstrate the trans-diaxial nature of the epoxide ring opening.     

Direct reductive amination using triethylsilane and catalytic bismuth(III) chloride

Direct reductive amination (DRA) using triethylsilane (TESH) and catalytic bismuth(III) chloride (BiCl₃) is described for the first time. The use of TESH and BiCl₃ provides easy handling, low cost, non-toxicity, and a mild Lewis acid activity, thereby meeting the demand for green and sustainable chemistry. The developed DRA is highly chemoselective and applicable to less-basic amines. The experimental results of this study revealed that the developed DRA could be catalyzed by BiCl₃, which was gradually reduced to Bi(0) or bismuth with a low valency by TESH, but TESCl, Bi(0), and Bi(0) with TESCl catalyzed the DRA to some extent.     

Les sels de bismuth(III), catalyseurs dans la réaction de clivage des éthers

Bismuth(III) salts as catalysts in the ether cleavage reaction. Bi (OTf)₃ and BiCl₃ react in catalytic quantity to cleaved the tertiobutyl–oxygen bound of the ethers 1, 3, 5.     

Bismuth trichloride-catalyzed oxy-Michael addition of water and alcohol to α,β-unsaturated ketones

An efficient method was developed for the conjugate addition of water to various α,β-unsaturated ketones by using bismuth(III) chloride as a catalyst. The reactions proceeded smoothly in the presence of a catalytic amount of BiCl₃ (20 mol%) in aqueous media to furnish a variety of synthetically useful β-hydroxyl ketones in moderate to good yields. Apart from water molecule, various alcohols could also be employed as nucleophiles to react with α,β-unsaturated ketones, leading to β-alkoxyl ketones in modest to high yields. In addition, the mild reaction conditions also entailed the conjugate addition reactions to proceed with the tolerance to a range of functional groups.     

Synthesis of 2,3-di(ω-hydroxyalkyl)quinolines from anilines and cyclic enols using sequential cycloaddition/aromatization reactions

A new synthetic protocol for the one-pot synthesis of 2-(4-hydroxybutyl)-3-(3-hydroxypropyl)quinolines and 3-(2-hydroxyethyl)-2-(3-hydroxypropyl)-quinolines based in the AB² imino-Diels-Alder reaction is reported. The protocol describes simple and efficient preparation of 2,3-disubstituted quinolines using a domino-sequential process and applying the chemical properties of cyclic enol ethers, such as 2,3-dihydrofuran and 3,4-dihydro-2H-pyran and diverse arylamines, through an imino-Diels-Alder process between an in situ generated 2-azadiene and another equivalent of the cyclic enol, catalyzed by BiCl₃, and followed by the aromatization (oxidation) process guided by the MnO₂.     

Darstellung von tris(o-deuterophenyl)bismut und bis(o-deuterophenyl)bismutbromid. Zuordnung des paramagnetisch verschobenen 1H-NMR-signals

(o-C₆H₄D)₃Bi was prepared from BiCl₃ and the Grignard reagent obtained from o-C₆H₄ClD (gained by solvolysis of the Grignard reagent from o-C₆H₄BrCl by CH₃COOD). Redistribution of (o-C₆H₄D)₃Bi and BiBr₃ afforded (o-C₆H₄D)₂-BiBr. It is demonstrated, that the paramagnetically shifted ¹H NMR signal observed in phenyl derivatives of bismuth has to be assigned to ortho-protons.     

Fourier-transform Raman and infrared spectra and normal coordinate analysis of (C6H5)2BiCl and [N(CH3)4]+[(C6H5)2BiCl2]−

The vibrational properties of the diphenylbismuth(III) chloride compounds (C₆H₅)₂BiCl and [N(CH₃)₄]⁺[(C₆H₅)₂BiCl₂]⁻ have been investigated. A comprehensive assignment of the fundamental modes in the measured Fourier-transform Raman and infrared spectra has been carried out. Normal coordinate calculations of these compounds based on new X-ray crystal structure data have been performed to identify the BiCl stretching and bending vibrations of both compounds. For [N(CH₃)₄]⁺[(C₆H₅)₂BiCl₂]⁻ in the solid state, the ν_s(BiCl₂) and ν_as(BiCl₂) occur at 215 cm⁻ (Raman) and 237 cm⁻ (Raman), respectively, in good agreement with the calculated wavenumbers. The force constant calculation yields a BiCl stretching force constant of 0.89 × 10² N m⁻¹.