Reaction Of BiCl3 Research Articles

Bis(acyl)phosphide - Ambidentate Ligands for the Synthesis of Group 14 and 15 Main Group Element Compounds.

The reactivity of the bis(acyl)phosphide ion [P(COR)2]- (BAP-, R = Ph, Mes) with silicon halides SiX4 (X = Cl, Br) and pnictogen chlorides ECl3 (E = As, Sb and Bi) was investigated. The reaction with SiX4 leads to the hexacoordinate silanes SiX2(BAP)2 in which BAP- is coordinated in the chelating k2-O,O' mode, analogously to acac-. Unexpectedly, the coordination behaviour of BAP- differs from the one of acac- in the interpnictogen compounds E(BAP)3 (E = As, Sb) in which the formation of a E-P bonds is favoured over k2-O,O' chelation via the oxygen centres. Finally, the reaction of BiCl3 with three equivalents of Na(BAP) leads to the formation of red, crystalline Bi2(BAP)4, an air stable dibismuthine, as product of a redox reaction.

Complexes of BiCl3 with hydrazone derived ligands: a Möbius-like discrete metal chelate versus a salt-like porous polymeric structure

Reaction of BiCl3 with hydrazone derived ligands yielded a new Möbius-like discrete metal chelate [Bi(LI)Cl3] and a salt-like porous polymeric structure ([H2LII]2[BiCl5]·EtOH)n.

Synthesis of Sb2Se3 and Bi2Se3 Nanoparticles in Ionic Liquids at Low Temperatures and Solid State Structure of [C4C1Im]3[BiCl6

Crystalline Sb2Se3 nanoparticles were prepared by reaction of SbCl3 with (Et3Si)2Se in the presence of oleylamine (OA) in the ionic liquid [C4C1Im]Cl, whereas the reaction of (Et3Si)2Se with [C4C1Im]3[BiCl6] (1), which was obtained from the reaction of BiCl3 with [C4C1Im]Cl and structurally characterized by single‐crystal X‐ray diffraction, yielded Bi‐rich Bi2Se3 nanoparticles. In contrast, the reaction of the reactive IL [C4C1Im]3[Bi3I12] with (Et3Si)2Se in the presence of oleylamine in [C4C1Im]I gave phase‐pure Bi2Se3 nanoparticles. The chemical composition of the nanoparticles was investigated by EDX, while possible surface contaminations were studied by XPS and IR spectroscopy. The morphology of the nanoparticles was studied by SEM and TEM.

Synthesis, crystal structure and spectroscopic studies of bismuth(III) complex with 2-substituted benzimidazole ligands

Reaction of BiCl3 with 2-(2-hydroxy-3-methoxyphenyl)benzimidazole (HL) in tetrahydrofuran (THF) under reflux gave mononuclear complex of formula [Bi(HL)2Cl3·H2O]. The binding interaction of the complex with bovine serum albumin (BSA) was investigated using the fluorescence quenching method. The experimental results showed that the complex could bind to BSA in the proportion of about 1:1. The binding reaction was spontaneous and hydrophobic force played major role in the reaction. The binding of the complex to BSA could change the microenvironment and conformation of BSA.

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.

Synthesis, Structure and Thermal Decomposition of the Bismuth Silyltellurolate Bi(TeSitBu2Ph)3

AbstractThe compound Bi(TeSitBu2Ph)3 (1) was obtained from the reaction of BiCl3 with tBu2PhSiTeSiMe3 in diethyl ether. The single crystal structure analysis revealed a trigonal pyramidal structure of the BiTe3 core and weak Bi···C(arene) contacts. Compound 1 was characterized by multinuclear NMR spectroscopy, IR spectroscopy and elemental analysis. Thermogravimetric experiments show that compound 1 decomposes with formation of Bi2Te3 or a mixture of elemental bismuth and Bi4Te3, depending on the pressure conditions.

Luminescent properties of 4,4-bipyridinium chlorobismuthate salt: Strong influence of solvation

Reaction of BiCl3 and 4,4-bipy in 2M HCl leads to the formation of 4,4-bipyridinium salt of binuclear chlorobismuthate complex (bipyH2)2[Bi2Cl10]·2H2O (1). When heated in air, 1 loses the solvate water molecules to give (bipyH2)2[Bi2Cl10] (2). The dehydration results in significant changes in luminescent behavior.

Borate-based ligands with two soft heterocycle/thione groups and their sodium and bismuth complexes

Two novel sodium complexes [NaBb] (1) (Bb = dihydrobis(2-mercapto-benzimidazolyl)borate) and [NaBt(Me)] (2) (Bt(Me) = dihydrobis(2-mercapto-4-methylthiazolyl)borate) have been prepared and characterized by using two heterocycles, 2-mercapto-benzimidazole and 2-mercapto-4-methylthiazole, as well as NaBH4 as precursors. The dipodal boron centred soft ligands Bb and Bt(Me) were prepared in situ. The reactivity of [NaBb] (1) and [NaBt(Me)] (2) towards Bi(III) ions has been studied. The resulting complex [BiBb2Cl] (3) contains an MS4 core with κ(3)-S,S,H coordination mode, while the complex [BiBt(Me)3] (4) with an MS6 core adopts a coordination mode κ(2)-S,S. A reaction of BiCl3 with the heterocyclic precursors 2-mercapto-benzimidazole (L(1)) and 2-mercapto-4-methylthiazole (L(2)) was also attempted; this afforded the monomeric [BiL(1)4Cl2][BiL(1)2Cl4] (5) and dimeric [BiL(2)2(μ-Cl)Cl]2 (6) bismuth complexes. The bismuth complexes possess distorted octahedral geometries except 3 for which a face-capped octahedron is found. The presence of (B)H···Bi interactions has been identified by X-ray diffraction in 3 with a H···Bi distance of 2.58(1) Å which is uniquely short and unprecedented. Two of the synthesized complexes (4 and 5) have been investigated by luminescence spectroscopy. They feature emission bands in the solid state at room temperature at 674 (4) and 586 nm (5), which are hypsochromically shifted in (frozen) ethanolic solutions at 77 K to 618 and 537 nm, respectively.

Coordination Complexes of Bismuth Triflates with Tetrahydrofuran and Diphosphine Ligands

The reaction of CH3OSO2CF3 (MeOTf) with BiBr3 in tetrahydrofuran (THF) yields (THF)2BiBr2(OTf) (1), which is converted to (dmpe)BiBr2(OTf) (2Br) upon displacement of the THF ligands with bis(dimethylphosphino)ethane (dmpe). The chloride derivatives (dmpe)BiCl2(OTf) (2Cl) and (dmpe)BiCl(OTf)2 (3) are obtained from the reaction of BiCl3 and dmpe with 1 and 2 equiv of Me3SiOSO2CF3 (TMSOTf), respectively. The complexes readily decompose in solution to give elemental bismuth and a mixture of products. The solid-state structures reveal dimeric units bridged by both triflate O-S-O interactions and weak Bi-X-Bi interactions (X = Cl, Br). Comparison of the solid-state structures illustrates that both cis and trans configurations of halides are possible in complexes of the form L2BiX2(OTf), depending upon the denticity of the ligand. The experimentally observed configurations are consistent with minima calculated at the MP2 level for the triflate-free cations in the gas phase. Examination of the MP2-calculated electronic structure of 3 reveals the presence of low-lying π-type orbitals that may result in Z-type ligand activity. However, the attempted coordination of 3 with the electron-rich metal center in K2PdCl4, via metal-to-ligand back-donation, leads instead to halide abstraction, giving [(dmpe)2Pd][(CH3CN)2Bi2Cl6(OTf)2] (8). The anion in 8 consists of two octahedral bismuth environments bridged along one edge by two triflate anions. The results illustrate new coordination chemistry for bismuth.

Synthesis, Characterization, and Antimicrobial and Antispermatogenic Activity of Bismuth(III) and Arsenic(III) Derivatives of Biologically Potent Nitrogen and Sulfur Donor Ligands

A series of Bi(III) and As(III) complexes with two N∩S donor ligands, 1-(4-chloro-2-oxo-2H-chromen-3-yl)-methylene)-thiosemicarbazide (L1H) and N′-[1-(2-oxo-2H-chrome-3yl-ethylidene]-hydrazinecarbodithionic acid benzyl ester (L2H) have been synthesized by the reaction of BiCl3 and Ph3As with ligands in 1 : 1 and 1 : 2 molar ratios. All the synthesized compounds were characterized by elemental analyses, melting point determinations, and a combination of electronic, IR, 1H NMR, 13C NMR spectroscopic techniques, and X-ray diffraction for structure elucidation. In order to evaluate the effect of metal ions upon chelation, both the ligands and their complexes have been screened for their antimicrobial activity against the various pathogenic bacterial and fungal strains. The metal complexes have shown to be more antimicrobial against the microbial species as compared to free ligands. Both the ligands and their corresponding metal complexes have been tested for their antifertility activity in male albino rats. The marked reduction in sperm motility and density resulted in infertility. Significant alterations were found in biochemical parameters of reproductive organs in treated animals as compared to control group. It is concluded that all these effects may finally impair the fertility of male rats.

ChemInform Abstract: The Bicyclic Polyselenium Cation Se102+ in the Structure of Se10[Bi4Cl14

AbstractSingle crystals of the new title compound are grown by reaction of BiCl3, Se, and SeCl4 in the temp.

ChemInform Abstract: C-F Bond Activation in the Reaction of BiCl3 with Sodium 2,4,6-Tris(trifluoromethyl)phenoxide.

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Synthesis, spectral study and antimicrobial activity of bismuth(III) 3(2′-hydroxyphenyl)-5-(4-substituted phenyl) pyrazolinates

Dichlorobismuth(III) pyrazolinates and chlorobismuth(III) dipyrazolinates of the type BiCl2(C15H12N2OX) and BiCl(C15H12N2OX)2 have been synthesized in dry benzene by reaction of BiCl3 and the sodium salt of pyrazoline in 1 : 1 and 1 : 2 molar ratios at elevated temperature [C15H12N2OX = 3(2′-hydroxyphenyl)-5-(4-X-substituted phenyl) pyrazoline and X = H in compounds 1, 5, CH3 in 2, 6, OCH3 in 3, 7 and Cl in 4, 8, respectively]. These newly synthesized derivatives have been characterized by elemental analysis (C, H, N, Cl and Bi), molecular weight measurements and spectral (IR, 1H NMR, 13C NMR) studies. Selected compounds screened against different bacteria and fungi show potential antibacterial and antifungal activities.

A facile and clean synthesis of pure bismuth sulfide iodide crystals

Pure BiSI (bismuth sulfide iodide) crystals were synthesized directly from the reaction of BiCl3, (NH2)2CS, and I2 through a mild hydrothermal process (160°C for 30 h) after simple filtration and washing. The as-prepared crystals were characterized by XRD, IR, XPS, and SEM. The band gap of the product was calculated to be about 1.8 eV from UV-Vis-NIR results. A possible reaction mechanism was proposed.

ＨＯＰＧへのＢｉＣｌ３及びＣｕＣｌ２インターカレーション

BiCl3 and CuCl2 reacted with HOPG (Highly Oriented Pyrolytic Graphite) in the various conditions. In the reaction of BiCl3 with CuCl2GIC, the only stage4 BiCl3GIC was obtained. In the reaction of CuCl2 and BiCl3 with HOPG, the coexistent substance of stage2 or 4 BiCl3GIC and stage2 or 4 CuCl2GIC was obtained. Composition of Cu and Bi was C20(CuCl2)0.74(BiCl3) in the case of mol ratio CuCl2:BiCl3=6:1 with the vacuum tube reaction, and was C11.76(CuCl2)2.08(BiCl3) in the case of 3:1.

Synthesis and characterization of aryl bismuth compounds using 2,4,6-triphenylphenyl as a bulky ligand

Reaction of BiCl3 with 2,4,6-triphenylphenyllithium in THF solution in a 1:3 ratio, or in toluene solution in a 1:2 ratio affords tris(2,4,6-triphenylphenyl)bismuth (1) and bis-(2,4,6-triphenylphenyl)bismuth chloride (2) respectively.1 can be recrystallized from THF; the crystal structure has been determined with a yellow crystal of composition (1)· 4.8THF (3). The comproportionation reaction of1 with BiCl3 in a 1:2 ratio, or of2 with BiCl3 in a 1:1 ratio gives 2,4,6-triphenylphenylbismuth dichloride (4). Reduction of2 with sodium in ammonia, with magnesium in THF, or with cobaltocene in toluene leads only to the isolation of 1,3,5-triphenylbenzene. Similarly, the reduction of4 with sodium in ammonia, or with magnesium in THF leads only to 1,3,5-triphenylbenzene as a decomposition product, however, reducing4 with cobaltocene in toulene affords1, the latter presumably resulting from a disproportionation reaction of a (not isolated) monovalent bismuth compound, e.g. “2,4,6-triphenylphenylbismuth (I)” (6).

Synthesis and Reactivity of “Bismuthinidene” Compounds and the Formation of Bi1 Chelate Complexes

Treatment of [Cp′Mn(CO)2THF] (Cp′C5H4Me) with BiCl3 at 20°C affords the “bismuthinidene” species [Cp′‐ (CO)2Mn]2BiCl (1b) and very small amounts of the “star‐type” compound [Cp′(CO)2Mn]3Bi2 (2). Higher yields of both compounds are obtained from the reaction of BiCl3 with [Na] [Cp′(CO)2MnSi(C6H5)3‐]. The molecular structure of 1b has been determined by an X‐ray diffraction study, which shows that the bismuth atom, having a trigonal‐planar coordination geometry, is bonded to two manganese atoms and one chlorine atom. There are weak interactions between the molecules of 1b in the solid state thus forming infinite spiral chains of “inidene” complexes. Compound 1b reacts with NaI to afford the iodine‐substituted species [Cp′(CO)2Mn]2BiI (3). Displacement of the chloride substituent from 1b by anionic chelating ligands AB− is also possible; 1b reacts with tropolonate, 8‐oxoquinolate, or 8‐mercaptoquinolate to form the bismuth(I) chelate compounds [CP′(CO)2Mn]Bi − AB (5a–c). The molecular structure of 5b has been determined by X‐ray crystallography which shows the bismuth atom in a pseudo trigonalbipyramidal geometry with the nitrogen atom lying above the plane defined by the two manganese and the oxygen atoms in an apical position. The molecular structure of 5c has also been determined, and although the numerical values are not very accurate, the coordination geometry of the bismuth atom is seen to be intermediate between pseudo trigonalbipyramidal and distorted tetrahedral. Abstraction of a chloride ligand from 1b by Me3SiOSO2CF3 affords the cationic cumulene‐type complex [Cp′(CO)2MnBiMn(CO)2Cp][CF3SO3] (6a). Dichloromethane solutions of 6a are not stable at room temperature but may be treated with 2,−2′‐bipyridine (bpy) to afford the stable adduct [{CP′(CO)2Mn}2Bi(bpy)][CF3SO3](7). The molecular structure of 7 has been determined by X‐ray analysis, and – similarly to 5c, although the numerical values are not very accurate – the overall geometry has been determined unequivocally. The bismuth atom is shown to have a distorted tetrahedral geometry, thus being ligated by two manganese atoms and the two nitrogen atoms of the bpy ligands.

Bi2IIIS34]4−, the Hitherto Sulfur‐Richest Complex

Sulfur complexes are always full of surprises: Reaction of BiCl3 with a polysulfide solution in acetonitrile furnishes the complex anion [Bi2S24]4− in which the Bi atoms are coupled by an S ligand. In each case two bidentate S ligands complete the square‐pyramidal coordination of the two Bi atoms. Neither a complex with coupled S ligands nor one with bidentate S ligands was previously known.

Synthesis, characterization, and crystal structure of µ-[1′-pyrrolidinecarbodithioato-S(Bi1,2)S′(Bi2)]-1,1,1,2,2-pentakis(1′-pyrrolidinecarbodithioato-SS′)dibismuth(III) ethanol (1/1) and of di-µ-chloro-bis[bis(1-pyrrolidinecarbodithioato-SS′)(thiourea-S)bismuth(III)

Reaction of BiCl3 and ammonium 1-pyrrolidinecarbodithioate, [NH4]pcdt, in CH2Cl2–EtOH (1 : 1) gave [{Bi(pcdt)3}2]·EtOH (1). Grinding BiCl3 and thiourea (tu) and reacting with [NH4]pcdt in CH2Cl2–EtOH (1 : 1) gave [{Bi(tu)(pcdt)2Cl}2](2). Compounds (1) and (2) have been characterized by single-crystal X-ray diffraction: both are triclinic, space group P, with for (1), a= 15.907(7), b= 14.429(7), c= 11.253(6)A, α= 82.84(8), β= 84.55(9), γ= 81.02(9)°, Z= 2 and R= 0.065. For (2), a= 10.491(6), b= 11.335(8), c= 8.81 2(7)A, α= 102.58(8), β= 107.44(6), γ= 97.44(8)°, Z= 1, and R= 0.028. In (1) the co-ordination around one bismuth atom is trigonal prismatic with an extraposition on a rectangular face, and pentagonal pyramidal around the other bismuth atom; a sulphur atom joins the two polyhedra with an asymmetric bridge. In (2) co-ordination at bismuth is pentagonal bipyramidal; two chlorines, one apical and one equatorial, are bridging so that two adjacent polyhedra share an edge.

X-Ray structural studies on free and co-ordinated 6-amino-8-mercaptopurinium cation in bismuth(III) complexes

Reaction of BiCl3 with 6-amino-8-mercaptopurine (amp) in HCl solution results in the formation of [Hamp]2[BiCl5(Hamp)]Cl·5H2O (2) and [Hamp][BiCl5(Hamp)]·2H2O (3). These complexes, together with the free ligand as a chloride, (1), have been characterized structurally by single-crystal X-ray diffraction showing that both the structures of (2) and (3) consist of [BiCl5(Hamp)]– anions, protonated ligand, and water molecules in different ratios; in addition, in (2) a Cl– is present. In the complex anions the bismuth atom is octahedrally surrounded by five chlorines and one ligand molecule co-ordinated via sulphur; in each of the three structures base stacking is present. All data were collected using Mo–Kα radiation. The space groups are C2/c for (1), P21 for (2), and P for (3). The final R indices were 0.031, 0.047, and 0.038 respectively.