BiCl3 Research Articles

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, structure and density functional theory calculations of a novel photoluminescent trisarylborane-bismuth(III) complex.

A novel trisarylborane-Bi(III) complex, tris(4-(dimesitylboryl)phenyl)bismuthine [Bi(PhBMes2 )3 ], in which (Ph=phenyl, and Mes=mesityl), was synthesized via the reaction of bismuth (III) chloride (BiCl3 ) with three equivalents of lithiated (4-bromophenyl)- dimesitylborane [BrPhBMes2 ]. The new trisarylbismuthine was characterized by elemental analysis, ultraviolet-visible (UV-vis) spectroscopy, and NMR (1 H and 13 C) spectroscopy. The molecular structure of Bi(PhBMes2 )3 in the solid state was determined using single-crystal X-ray diffraction analysis, which showed short intermolecular C-H···H-C contact. The complex is a fluorescent emitter (λmax =395nm) at room temperature and a phosphorescent emitter (λmax =423nm) at 77K, which displayed a long lifetime of 495ms. The UV-vis transitions were investigated using density function theory (DFT) and time-dependent (TD)-DFT calculations. Natural bond orbital analysis showed that the bismuth (III) center was mainly Lewis acidic in nature.

Active bismuth mediated allylation of carbonyls/N-tosyl aldimines and propargylation of aldehydes in water

Active bismuth is synthesized by the chemical reduction of bismuth trichloride using freshly prepared sodium stannite solution as the reducing agent at room temperature. The as-synthesized active bismuth is applied as a reagent for the synthesis of homoallyl alcohol/homopropargyl alcohol from allyl bromide/propargyl bromide and carbonyl compounds in water at $$50\,{^{\circ }}\hbox {C}$$ . The homoallyl amines are also synthesized from N-tosyl aldimines and allyl bromide using active bismuth reagent in good yields. No assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere is required for this reaction. The waste bismuth material obtained after the completion of the organic reaction can be reduced to active bismuth by sodium stannite solution and successfully reused for mediating the allylation of aldehydes. Synopsis Active bismuth mediated allylation/crotylation of aldehydes is developed in water to get homoallyl alcohols. The method is also applied for the allylation of N-tosyl aldimines and propargylation of aldehydes in water to achieve the homoallyl amines and homopropargyl alcohols, respectively. The reactions do not require the assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere.

BiCl3-modified perlite as an effective catalyst for selective organic transformations: a green protocol

A new perlite supported Bismuth Chloride (BiCl3) was used as an efficient heterogeneous catalyst for the synthesis of heterocyclic compounds viz., quinoxalines and dihydropyrimidinones. Fourier-transform infrared spectroscopy (FT–IR), scanning electron microscopy, energy dispersive spectra, X-ray diffractometry, thermogravimetric analysis and Brunauer–Emmett–Teller surface area analytical techniques were employed to characterize the prepared catalyst. Initially, the catalytic activity of the prepared BiCl3-Perlite was tested towards synthesis of simple quinoxaline derivatives at room temperature. The effect of solvent in the preparation of quinoxaline was also examined. The formed products were confirmed by their physical (melting point) and spectral data (FT–IR, 1H and 13C-NMR). In order to implement the activity of the BiCl3-Perlite catalyst, a multicomponent reaction was adopted for synthesis of dihydropyrimidinones under solvent free conditions in a micro oven. The use of recyclable heterogeneous solid acid catalyst makes the reaction simple with minimum chemical waste, shorter reaction time, easy workup and products in good yield.

SiO2-BiCl3 as Heterogeneous Catalyzed Synthesis of 6-Methyl-2-aryl-4,5-dihydropyridazin-3(2H)-one Derivatives

A mild and highly efficient stereoselective reaction using silica supported bismuth(III) chloride (SiO2-BiCl3) has been successfully employed in the synthesis of 6-methyl-2-aryl-4, 5-dihydropyridazin-3(2H)-one derivatives (3a-o) with a variety of phenyl hydrazines (1a-o) bearing either electron withdrawing or donating functional groups and 4-pentynoic acid (2). The catalyzed reaction proceeded smoothly under room temperature in THF to give the corresponding 3a-o derivatives in good to excellent yields. The 3a-o derivatives have been characterized by IR, 1H NMR, 13C NMR, mass and elemental analysis. The use of this approach allowed us to rapidly screen a selection of conditions and quickly confirm the viability of preparing the target 3a-o derivatives in short reaction times.

Synthesis, crystal structure and photochromic property of a phenethyl viologen bismuth(III) chloride

Viologen bismuthate halides generally show photochromic properties. In the present work, phenylethyl alcohol was introduced into chloro bismuthates in the hope to prepare photochromic crystalline materials and finally a photochromic inorganic-organic hybrid, (PeV)3(Bi2Cl9)2 (1), based on an in situ generated PeV2+ cation (PeV2+ = phenethylviologen = N,N′-diphenethyl-4,4′-bipyridinium), has been obtained, whose microstructure contains a discrete dimer [Bi2Cl9]3– counterion identified by single crystal X-ray diffraction. More importantly, 1 exhibits a typical photochromic behavior, which can be mainly attributed to the reversible inter-conversion between the monocation viologen radical [PeV]+• and the viologen dication [PeV]2+.

Anionic Bismuth(III) chloride cluster with diselenide countercations: Application in C-S cross coupling reactions

The first weakly coordinating anion (WCA) with reactive p-block cation (rPBC) type of [(Bi4Cl16)4-{(LSeSeL)2+}2], L = 1,3-bis(2-benzhydryl-4,6-dimethylphenyl)-1H-imidazole-2(3H), ion pair is reported. The tetranuclear anionic bismuth(III) cluster shows a new type of ladder structure with two different types of Bi(III) coordination modes. In the solid state structure, the tetranuclear bismuth(III) cluster is sandwiched by two diselenide cations through hydrogen bonding interactions. Besides, this ion pair has been efficaciously employed as catalyst in C-S cross-coupling reactions under optimized reaction condition. This ion pair depicted a wide range of substrate scope with different thiols and aryl halides.

Antimicrobial Effects of Silver(I) and Bismuth(III) Complexes with Secnidazole‑Derived Schiff Base Ligands: the Role of the Nitro Group Reduction

[Ag(HL)NO3] complexes (1-4) were obtained with (E)-N’-(1-(2-methyl-5-nitro-1H-imidazol-1-yl)propan-2-ylidene)acetohydrazide (HL1); (E)-N’-(1-(2-methyl-5-nitro-1H-imidazol-1-yl)propan-2-ylidene)benzohydrazide (HL2); (E)-2-(1-(2-methyl-5-nitro-1H-imidazol-1-yl)propan-2-ylidene)hydrazinecarbothioamide (HL3) and (E)-N-methyl-2-(1-(2-methyl-5-nitro-1H-imidazol-1-yl)propan-2-ylidene)hydrazinecarbothioamide (HL4) secnidazole-derived Schiff bases. In addition, complexes [Bi(HL3)Cl3] (5) and [Bi(HL4)Cl3] (6) were also prepared. The silver(I) complexes (1-4) showed antifungal activity against Candida fungal strains while the uncomplexed ligands and the bismuth(III) complexes (5-6) were inactive, suggesting that the antifungal effects are probably due to the presence of silver. Although the Schiff base ligands and complexes (1-6) revealed to be inactive against Gram-positive and Gram-negative aerobic bacteria, all compounds exhibited potent antimicrobial effects against several anaerobic bacterial strains, indicating that their mode of action probably involves anaerobic bio reduction of the nitro group, with formation of metabolites which are toxic to the microorganisms. Electrochemistry studies showed that bio reduction of the nitro group is favored in complexes (1-6) in comparison to the free ligands, which might, at least in part, explain their increased antimicrobial effects.

Transmetallation of bis(6-diphenylphosphinoxy-acenapth-5-yl)mercury with tin tetrachloride, antimony trichloride and bismuth trichloride.

We recently communicated (Angew. Chem. Int. Ed., 2018, 57, 5917-5920) the transmetallation of [6-Ph2P(O)-Ace-5-]2Hg (1) with Pb(OAc)4, which, after work-up with HCl in Et2O, provided the first aryl lead trichloride, 6-Ph2P(O)-Ace-5-PbCl3 (2), and 6-Ph2P(O)-Ace-5-HgCl (3). With LiCl, 1 forms a complex, [{[6-Ph2P(O)-Ace-5]2Hg}2Li]Cl (1a), that shows no reactivity towards Pb(OAc)4 anymore, which highlights the role of the intramolecularly coordinated P(O) functionality in transmetallation. In this work, we have broadened the scope of the transmetallation reagent by the reaction of 1 with SnCl4, SbCl3 and BiCl3 giving rise to the formation of 6-Ph2P(O)-Ace-5-SnCl3 (4), 6-Ph2P(O)-Ace-5-SbCl2 (5) and 6-Ph2P(O)-Ace-5-BiCl2 (6), respectively. The high Lewis acidity permits 4 and 5 to undergo complexation with THF, whereas no such complexes were formed with 2 and 6. The molecular structures of 1a, 3, 4, 4·THF, 5, 5·THF and 6 were established by X-ray crystallography. The different P-O distances of 2, 4, 4·THF, 5, 5·THF and 6, reflecting the relative strength of the P(O)E coordination (E = Pb, Sn, Sb, Bi), were discussed. The nature of the P(O)E interactions of 2, 4, 4·THF, 5, 5·THF and 6 was studied using a set of real-space bond indicators (RSBIs).

Iron-mediated highly diastereoselective allylation of carbonyl compounds with cyclic allylic halides

An efficient iron-mediated highly diastereoselective allylation reaction of carbonyl compounds with cyclic allylic halides using a catalytic amount of bismuth(iii) chloride is reported.

Electrode Potentials of Bismuth in a Mixture of Potassium and Lead Chlorides

The equilibrium potentials of Bi in a KCl–PbCl2–BiCl3 melt were measured by the EMF method at different temperatures and bismuth chloride contents. Empirical equations of isotherms and polytherms of the equilibrium potentials of bismuth were obtained. The conventional standard potentials of Bi in a molten mixture of potassium and lead chlorides were calculated. The changes in the Gibbs energy during the formation of bismuth trichloride from the elements in the melt were calculated. The coefficients of metal separation from alloys were estimated. The results indicate that it is promising to develop a technology for electrolytic processing of secondary raw materials for separating lead and bismuth in chloride melts.

Relay Catalysis of Bismuth Trichloride and Byproduct Hydrogen Bromide Enables the Synthesis of Carbazole and Benzo[α]carbazoles from Indoles and α‐Bromoacetaldehyde Acetals

AbstractBenzo[α]carbazoles were synthesized from 2‐phenylindoles and α‐bromoacetaldehyde using bismuth trichloride as a catalyst. The reaction was triggered by a bismuth trichloride‐catalyzed Friedel‐Crafts alkylation of these two precursors, which provided a tryptaldehyde intermediate that underwent intramolecular olefination to form the final product. Interestingly, the HBr byproduct generated in the upstream step of the reaction catalyzed the following downstream reaction steps, thus creating a byproduct‐participated relay catalytic process. Motivated by this mechanism, we developed a three‐component reaction of indole, α‐bromoacetaldehyde acetal, and 1,3‐dicarbonyl compounds. This study offers a straightforward method for synthesizing substituted carbazoles.magnified image

Thermodynamic Simulation of Simultaneous Extraction of Metals During Waste Processing Industry

The depletion of ores, a rise in the cost of their extraction, enrichment and processing led in the last 10‒15 years to a sharp rise in prices for tungsten products. Therefore, the processing began to involve technogenic waste ‒ dumps of enrichment factories and metallurgical industries, which previously did not represent the commercial interest on this case, we present the information on the results of the thermodynamic modeling of tungsten and bismuth chloride distillation in the processing of industrial waste using NaCl as a chlorinating agent. To calculate thermodynamic models for the associated extraction of tungsten and bismuth from industrial wastes, the ASTRA-4 software complex was used which created on basis of the maximum entropy of all possible reactions occurring during the retrieval of refractory metals from waste. Thus, the calculations carried out and experimental studies of the main provisions of thermodynamic calculation have shown the possibility of using NaCl salts for bismuth chlorination. At the same time, the maximum degree of sublimation of bismuth not be lower than 98% and can be achieved even at a temperature of 1200 K and a pressure of 0.01–0.1 MPa. At the same time, NaCl is not an effective chlorinating agent for retrieving of tungsten during high-temperature processing of industrial wastes.

Design and Synthesis of 1D-Polymeric Chain Based [(CH3NH3)3Bi2Cl9]n Perovskite: A New Light Absorber Material for Lead Free Perovskite Solar Cells

Although traditional perovskite solar cells have made tremendous progress in terms of efficiency, the presence of toxic lead has restricted their commercialization. Herein, we report the first example of a facile synthesis and a newly designed highly stable lead free methylammonium bismuth chloride in the form of 1D-polymeric chain based perovskite. The formation of a 1D-polymeric chain with formula [(CH3NH3)3Bi2Cl9]n (1) has been authenticated by its single crystal X-ray diffraction (SCXRD) studies. The lead free 1 has been employed as an alternative to the traditional CH3NH3PbX3 perovskite with an excellent open circuit voltage of 430 mV.

In situ synthesis of C3N4/Bi2S3 composites with enhanced photocatalytic degradation performance under visible light irradiation

Carbon nitride/bismuth sulfide (C3N4/Bi2S3) nanocomposites were prepared by a facile one‐step in situ calcination method using ammonium thiocyanate and bismuth chloride as reagents. The crystal structure, composition, and morphology of the nanocomposites were characterized by X‐ray diffraction (XRD), Fourier transform infrared (FT‐IR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The photocatalytic degradation of rhodamine B (RhB) was carried out to evaluate the photocatalytic activity of the nanocomposites under visible light irradiation. The as‐prepared C3N4/Bi2S3 nanocomposites displayed enhanced visible light absorption. These photocatalysts exhibited superior photodegradation performance under visible light irradiation compared to pure C3N4. Meanwhile, the C3N4/Bi2S3 nanocomposites exhibited remarkably stable photocatalytic efficiency after five cycles of photodegradation of RhB. The C3N4/Bi2S3 heterostructure improved the separation and transfer efficiency of the photogenerated electron–hole pairs. It played an important role for the enhanced photocatalytic performance of the nanocomposite photocatalysts.

The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver-Bismuth Halide Compositions.

Replacing lead in halide perovskites is of great interest due to concerns about stability and toxicity. Recently, lead free double perovskites in which the unit cell is doubled and two divalent lead cations are substituted by a combination of mono- and trivalent cations have been synthesized as bulk single crystals and as thin films. Here, we study stability and optical properties of all-inorganic cesium silver(I) bismuth(III) chloride and bromide nanocrystals with the double perovskite crystal structure. The cube-shaped nanocrystals are monodisperse in size with typical side lengths of 8 to 15 nm. The absorption spectrum of the nanocrystals presents a sharp peak, which we assign to a direct bismuth s-p transition and not to a quantum confined excitonic transition. Using this spectroscopic handle combined with high-resolution transmission electron microscopy (TEM) based elemental analysis, we conduct stoichiometric studies at the single nanocrystal level as well as decomposition assays in solution and observe that Ag+ diffusion and coalescence is one of the pathways by which this material degrades. Drying the nanocrystals leads to self-assembly into ordered nanocrystal solids, and these exhibit less degradation than nanocrystals in solution. Our results demonstrate that Cs2AgBiX6 (X = Cl, Br) nanocrystals are a useful model system to study structure-function relationships in the search for stable nontoxic halide perovskites.

Synthesis, Growth, and Characterization of a New Thiourea and Bismuth Chloride Complex with Excellent Nonlinear Optical Properties

Crystals of a new organometallic nonlinear optical (NLO) compound, di-μ-chloro-bis[chlorotri(thiourea)bismuth(III)]-pentachloro(thiourea)bismuth-ate(III) (DCBPB), have been successfully grown from formic acid aqueous solutions of thiourea and bismuth chloride by a slow evaporation technique. The crystal structure and atomic composition of DCBPB have been confirmed by single crystal X-ray diffraction (SCXRD), Fourier transform infrared spectra, and elemental analysis. The SCXRD results proved that DCBPB crystallizes in triclinic space group P1 with unit cell dimensions of a = 7.0606(2) Å, b = 8.8106(4) Å, c = 16.3247(8) Å, α = 99.242(4)°, β = 95.309(3)°, γ = 105.856(3)°, and Z = 2. DCBPB crystal exhibits excellent transmittance from 500 to 2500 nm and green fluorescence with maximum emission at 508 nm. The thermogravimetric-differential scanning calorimetry (TG-DSC) analysis indicates that a solid-phase reaction took place at 170.1 °C, whereas the decomposition temperature of the crystal material was 189 °C. The NLO property obtained by the Kurtz powder test showed that the second harmonic generation efficiency of DCBPB crystal is two-seventh of KDP crystal.

Trapping of the N,C,N-chelated organobismuth(I) compound, [2,6-(Me2NCH2)2C6H3]Bi, by its coordination toward selected transition metal fragments

The in situ reduction of the N,C,N-chelated bismuth(III) chloride (ArBiCl2) (where Ar = 2,6-(Me2NCH2)2C6H3) with 2 equivalents of K[B(s-Bu)3H] produced an unstable bismuth(I) compound ArBi (1) that was trapped by its coordination toward suitable transition metal fragments. Using this strategy a set of complexes with Group 6 metal carbonyls was obtained, i.e. [ArBiM(CO)5] (1-M; where M = Cr, Mo, W). The treatment of 1 with [Fe2(CO)9] provided the expected complex [ArBiFe(CO)4] (1-Fe) along with [ArBi(Fe(CO)4)2] (1-Fe2) as a minor by-product. By contrast, the reaction of 1 with the dinuclear complex [Co2(CO)8] furnished ionic complex [(ArBi)2Co(CO)3][Co(CO)4] (1-Co). All compounds were characterized using 1H and 13C{1H} NMR, IR and Raman spectroscopy. Molecular structures of 1-Cr, 1-Fe, 1-Fe2 and 1-Co were determined by the help of single-crystal X-ray diffraction analysis.

Synthesis, characterization and cytotoxic properties of bismuth(III) chloride complexes with heterocyclic thioamides

Abstract Bismuth(III) complexes of the formulae [BiCl3(MBZT)2] ·H2O} (1), {[BiCl2(µ2-Cl)(MMI)2]2·(CH3)2CO} (2), {[BiCl3(µ2-S-PYT)(PYT)]2} (3) {([BiCl2(MBZIM)4]+)·2(Cl-)·(H3O+) ·2H2O} (4) and [BiCl3(tHPMT)3] (5) (where MBZT: 2-mercaptobenzothiazole, MMI: 2-mercapto-1-methylimidazole, PYT: 2-mercaptopyridine, MBZIM: 2-mercaptobenzimidazole, tHPMT: 2-mercapto-3,4,5,6-tetrahydro-pyrimidine) are reported. The compounds were characterized by spectroscopic techniques including FT-IR, FT-Raman, UV-Vis, 1H-,13C-NMR spectroscopies, TG-DTA, e.a, molar conductivity and by single-crystal X-ray diffraction analysis. While 1, 4 and 5 are mononuclear compounds, 2 and 3 are dinuclear complexes in which the two Bi3+ ions are bridged through Cl- and SR groups respectively. Interestingly, 3 is the first example of dinuclear Bi3+ complex containing two Bi-(μ-SR)-Bi bridges between the two metal centers formed by covalent bonds. Compounds 1–5 were evaluated for their in vitro cytotoxic activity against human adenocarcinoma cervix (HeLa) and breast (MCF-7) cells. The toxicity of 1–5 was evaluated on normal human fetal lung fibroblast cells (MRC-5). The influence of 1–5, on the catalytic peroxidation of the linoleic acid by the enzyme lipoxygenase (LOX) was determined experimentally.

Physicochemical properties of Bi-containing ionic liquid analogs based on choline chloride

The preparation and characterization of homogeneous and colorless ionic liquid analogs(ILAs) containing choline chloride(ChCl), malonic acid and bismuth chloride were investigated. The structure of the above mixture was preliminarily analyzed, and then the physicochemical properties including viscosity, conductivity and density were investigated as functions of temperature and composition. Additionally, the thermal stability of the ILAs and the electrochemical behavior of Bi3+ ions in the medium were studied. Structure analysis reveals that the synthesis of deep eutectic solvents(DESs) is closely related to the formation of hydrogen bonds between malonic acid and ChCl, with their viscosity, conductivity and density being greatly dependent on the temperature and composition. Thermogravimetric analysis demonstrates that the ILAs are very stable between room temperature and 398.15 K. And the electrochemical experiments indicate that the bismuth films can be successfully deposited from this ILAs and the deposition mechanism of bismuth is a rather irreversible process. The surface morphology of bismuth films deposited on Cu substrates was very compact and smooth. Thus, ChCl-malonic acid DESs were shown to be a good alternative to aqueous solvents for various deposition-related applications.