Determination of Lead(II) Using Screen‐Printed Bismuth‐Antimony Film Electrode

This work presents a disposable bismuth‐antimony film electrode fabricated on screen‐printed electrode (SPE) substrates for lead(II) determination. This bismuth‐antimony film screen‐printed electrode (Bi‐SbSPE) is simply prepared by simultaneously in situ depositing bismuth(III) and antimony(III) with analytes on the homemade SPE. The Bi‐SbSPE can provide an enhanced electrochemical stripping signal for lead(II) compared to bismuth film screen‐printed electrodes (BiSPE), antimony film screen‐printed electrodes (SbSPE) and bismuth‐antimony film glassy carbon electrodes (Bi‐SbGC). Under optimized conditions, the Bi‐SbSPE exhibits attractive linear responses towards lead(II) with a detection limit of 0.07 µg/L. The Bi‐SbSPE has been demonstrated successfully to detect lead in river water sample.     

Organobismuth(III) and organobismuth(V) carboxylates and their evaluation as paint driers

A range of bismuth and organobismuth carboxylates has been prepared e.g. Bi(carboxylate)₃; PhBi(carboxylate′)₂; and Ph₃Bi(carboxylate″)₂ where carboxylate=octanoate, i.e. 5-ethylhexanoate; carboxylate′=acetate and monomaleate; carboxylate″=acetate, propionate, benzoate, 5-ethylhexanoate, and 0.5 oxalate. A combination of IR (solid) and NMR (solution) studies suggests that in the case of the bismuth(V) compounds the carboxylates may be inequivalent in the crystalline forms but equivalent in solution. The compounds have been tested as driers in two paint formulations, Synolac 50W (linseed-based) and Sorbal P470 (linoleic-rich). Although initially promising results were obtained for Synolac 50W, the shelf life of the bismuth driers was poor. With Sorbal P470, bismuth driers were inferior to established formulations. However, a combination of Bi(OOCH₇H₁₅)₃ with tris(diethyldithiocarbamato)-bismuth(III) out-performed established driers.     

Extraction and separation of bismuth(III)

Separation of bismuth from beryllium, lead, iron(III), indium, scandium, lanthanum, antimony(III), zirconium, titanium, thorium, vanadium(V), molybdenum(VI), uranium (VI) and chromium(VI) is achieved by selective extraction of bismuth from 0.1M sodium salicylate solution (adjusted to pH 7) into mesityl oxide (MeO). The extracted species is Bi (HOC(6)H(4)COO)(3).3MeO. The results are accurate within +/- 0.5%, with a standard deviation of 0.8%. The separation and determination of bismuth takes only 15 min.     

Isolation of Cyclic(Alkyl)(Amino) Carbene–Bismuthinidene Mediated by a Beryllium(0) Complex

The long-sought carbene–bismuthinidene, (CAAC)Bi(Ph), has been synthesized. Notably, this represents both the first example of a carbene-stabilized subvalent bismuth complex and the extension of the carbene-pnictinidene concept to a non-toxic metallic element (Bi). The bonding has been investigated by single-crystal X-ray diffraction studies and DFT calculations. This report also highlights the hitherto unknown reducing and ligand transfer capability of a beryllium(0) complex.     

固固相反应合成牛磺酸水杨醛钾与锑、铋的配合物

合成了牛磺酸水杨醛钾,并采用室温固固相反应法合成了牛磺酸水杨醛钾与三氯化锑和三氯化铋的配合物,其组成为:K2MC18H20O8N2S2 (M = Sb, Bi)。两种配合物的晶体结构均属于单斜晶系,锑配合物的晶胞参数为:a = 1.2869 nm, b = 1.7636 nm, c = 1.9917 nm, β= 93.79埃活榕浜衔锏木О问篴 = 1.4770 nm, b = 2.0334 nm, c = 2.0149 nm, β= 94.05。红外光谱表明N、Cl原子参与了配位,中心离子的配位数为5。     

固固反应合成三碘化锑、三碘化铋的硫脲配合物(英文)

通过三碘化锑和三碘化铋与硫脲间的室温固固反应合成了三碘化锑、三碘化铋的硫脲配合物 ,其组成通式为 :M(CS(NH2 ) 2 ) 3 I3 (M =Sb ,Bi) .两种配合物的晶体结构均属于单斜晶系 ,锑配合物Sb(CS(NH2 ) 2 ) 3 I3 的晶胞参数为 :a =1.4 772nm ,b=1.6 5 82nm ,c =2 .0 6 74nm ,β =90 .81°,铋配合物Bi(CS(NH2 ) 2 ) 3 I3 的晶胞参数为 :a =1.4 0 10nm ,b =2 .0 16 8nm ,c =2 .0 397nm ,β =90 .84° .远红外光谱表明硫脲中的N原子而非硫原子参与了配位     

固固反应合成三碘化锑、三碘化铋与硫脲配合物

通过三碘化锑和三碘化铋与硫脲间的室温固固反应合成了三碘化锑、三碘化铋的硫脲配合物 ,其组成为 :M[CS( NH2 ) 2 ]3 I3 ( M=Sb,Bi)。两种配合物的晶体结构均属于单斜晶系 ,锑配合物 Sb[CS( NH2 ) 2 ]3 I3 的晶胞参数为 :a=1 .4 772 nm,b=1 .6 5 82 nm,c=2 .0 6 74 nm,β=90 .81°,铋配合物 Bi[CS( NH2 ) 2 ]3 I3 的晶胞参数为 :a=1 .4 0 1 0 nm,b=2 .0 1 6 8nm,c=2 .0 397nm,β=90 .84°。远红外光谱表明硫脲中的 N原子而非硫原子参与了配位     

Determination of total antimony(III,V) by square-wave anodic stripping voltammetry with in situ plated bismuth-film electrode

A sensitive and reliable method is described for the determination of total Sb(III,?V) at traces levels by Osteryoung square-wave anodic stripping voltammery (OSWASV). This method is based on the co-deposition of Sb(III,?V) with Bi(III) onto an edge-plane pyrolytic graphite substrate at an accumulation step. OSWASV studies indicated that the co-deposited antimony was oxidised with anodic scans to give an enhanced anodic peak at about 450?mV vs. Ag/AgCl (sat. KCl). The anodic stripping peak current was directly proportional to the total concentration of antimony in the ranges of 0.01–0.10?µg?L^?1, 0.10–1.0?µg?L^?1 and 1.0–18.0?µg?L^?1 with correlation coefficient higher than 0.995 when 2.0?mol?L^?1 hydrochloric acid was used. The detection limits calculated as S/N?=?3 was 5.0?ng?L^?1 in 2.0?mol?L^?1 hydrochloric acid at 180?s deposition time. The relative standard deviation was 5% (n?=?6) at 0.10?µg?L^?1 level of antimony. The analytical results demonstrate that the proposed method is applicable to analyses of real water samples.     

Über bismut-haltige heterocyclen: I. Methylierte und phenylierte bismocane,intra- und intermolekulare koordinationserhöhung an bismut(III)

Methyl and phenyl oxadithia and trithiabismocanes have been synthesized from methyl or phenyl diethoxybismutane and the respective dithiol. The light-sensitive compounds have been investigated by mass, vibrational and ¹³C NMR spectra: ν(BiMe) 470–460, ν(BiS₂) 300–240 cm^?1; δ(¹³Me) ?12 ppm. The crystal structure of 5-phenyl-1,4,6,5-oxadithiabismocane has been determined (R = 0.056). The eight-membered ring has the chair-chair conformation. Besides three direct bonds (BiPh 225(2), BiS 256.0(2) and 260.2(3) pm) there are one transannular (Bi?O 297(1) and two intermolecular contacts (Bi ?S 344.0(3) and 350.9(3) pm) to bismuth in resulting a ψ-monocapped octahedral sphere of coordination. These polyhedra are connected in sharing two different edges, and the crystal structure exhibits double chains of molecules.     

Liquid-liquid extraction of arsenic(III), antimony(III) and bismuth(III) with potassium ethyl xanthate

Summary Methods are described for quantitative extraction of arsenic(III), antimony(III) and bismuth(III) with potassium ethyl xanthate-carbon tetrachloride. The optimum acidity conditions are 0.1–0.2 M hydrochloric acid for arsenic, 1.8–2.5 M hydrochloric acid for antimony and p_H 1.5–4.0 for bismuth. From the organic extracts arsenic and antimony are estimated by conventional iodometric methods while bismuth is determined spectrophotometrically at 400 nm. The effect of acidity, reagent concentration, period of extraction and diverse ions are discussed. The infra-red spectra are also described.

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Zusammenfassung Verfahren für die Extraktion von As(III), Sb(III) und Bi(III) mit Kaliumäthylxanthat/Tetrachlorkohlenstoff werden beschrieben. Die optimalen Aciditätsbedingungen sind: 0,1–0,2 M HCl für As, 1,8–2,5 M HCl für Sb und p_H 1,5–4,0 für Bi. As und Sb werden nach Entfernung des organischen Lösungsmittels jodometrisch bestimmt; Bi wird im gelb gefärbten Extrakt spektrophotometrisch bei 400 nm bestimmt. Der Einflu\ der Acidität, der Reagenskonzentration, der Schütteldauer und verschiedener Fremdionen auf die Extraktion wird besprochen. Die IR-Spektren der gebildeten Komplexe werden diskutiert.

     

Synthesis and Crystal Structure of the Mixed-quadriligand Bismuth Complex [Bi(S_2CNEt_2)_2(NO_3)]·[1,10-Phen]

1 INTRODUCTION Some reports on the syntheses and crystal struc-tures of organotin(IV) dithiocarbamate complexes haveappeared in the previous literatures[1～3], but the bis-muth(Ⅲ) complexes with dithiocarbamate have beenscarcely studied[4]. Due to the n…     

Synthesis and structure of triphenylbismuth bis(1-adamantanecarboxylate)

Triphenylbismuth bis(1-adamantanecarboxylate) was synthesized by reacting triphenylbismuth with 1-adamantanecarboxylic acid in the presence of hydrogen peroxide. In the complex, the coordination sphere of a bismuth atom is a trigonal bipyramid with C(Ph) atoms in the equatorial plane and O atoms in the apical positions. The Bi-C bond lengths are 2.213(4) Å (two bonds) and 2.222(5) Å; two Bi-O bond lengths are 2.306(3) Å. The Bi…O(=C) donor-acceptor interactions (2.716(3) Å) occur in the molecule. The equatorial CBiC angle on the side of the Bi…O(=C) contact is 157.1(2)°.     

Synthesis and characterization of triorganoantimony(V) complexes with bidentate ligands

Monochelated organoantimony(V) complexes of the type R₃Sb(OMe)L, where R = Me or Ph, and L is the anion of acetylacetone, 8-hydroxyquinoline, salicylaldehyde, o-hydroxyacetophenone or 2-hydroxy-1-naphthaldehyde have been obtained from triorganoantimony(V) dibromide and the sodium derivative of the ligands in a benzene-methanol mixture. Molecular weight determination in benzene reveals the monomeric nature of these complexes. IR and NMR data suggest that L acts as a bidentate ligand giving an octahedral environment for the antimony atom.     

Hydroxonium-hexachloroantimonate(V)

Hydroxonium Hexachloroantimonates(V) The hydroxonium hexachloroantimonates(V) H₅O₂⊕SbCl₆? (I), H₇O₃⊕SbCl₆? (III), H₉O₄⊕SbCl₆? (V) as well as the deuterated compounds D₅O₂⊕SbCl₆? (II), D₇O₃⊕SbCl₆? (IV) and D₉O₄⊕SbCl₆? (VI) were prepared by reaction of hydrogen chloride resp. deuterium chloride with water addition compounds of antimony(V) chloride. The i.r. spectra are discussed.     

Spectrophotometric study of the reaction of bismuth(III) with Xylenol Orange

The reaction between bismuth(III) and Xylenol Orange (XO) has been investigated by spectrophotometry. It has been established that bismuth(III) and Xylenol Orange form complex compounds with compositions Bi(III):XO = 1:1 (up to pH 1) and Bi(III):XO = 1:2 (above pH 1) which have absorption maxima at 550 and 500 nm respectively. The formula of the 1:1 complex is [Bi(H(3)R)] whereas the 1:2 complex can take one of the following forms: [Bi(H(4)R)(2)](1-), [Bi(H(4)R)(H(3)R)](2-) and [Bi(H(3)R)(2)](3-). If the values for pK(Bi(H(3)R)) and pK(Bi(H(3)R)(2)) respectively are 9.80 +/- 0.03 and 15.53 +/- 0.03 at a constant ionic strength of 1.0.     

Electrochemical transformations of antimony(V) complexes containing tridentate O,N,O-donor ligands

Electrochemical transformations of antimony(V) complexes containing a tridentate redoxactive ligand, N,N-bis-(2-hydroxy-di-3,5-tert-butylphenyl)amine: R ₃Sb(Cat-NH-Cat) (R = (1) Ph; (2) Et), (3) Et₂Sb(Cat-N-Cat)) are studied. Electrochemical oxidation of complexes 1, 2 occurs irreversibly leading to formation of unstable radical cations. The next stage is the chemical process resulting in formation of neutral paramagnetic compounds. The Et₂Sb(V)(Cat-N-Cat) complex is characterized by two reversible anodic redox processes corresponding to a change of in the ligand redox level. Stable paramagnetic derivatives are formed as a result of electrochemical oxidation of compounds 1, 3; this allows considering these compounds as potential radical scavengers. Interaction of complex 1 with electrogenerated superoxide radical anion led to formation of paramagnetic reaction products.     

Rhenium(V) and technetium(V) complexes with phosphoraneimine and phosphoraneiminato ligands

Air-stable rhenium(V) nitrido complexes are formed when [ReOCl3(PPh3)2], [NBu4][ReOCl4], or [NBu4][ReNCl4] are treated with an excess of silylated phosphoraneiminates of the composition Me3SiNPPh3 or Ph2P(NSiMe3)CH2PPh2 in CH2Cl2. Complexes of the compositions [ReNCl(Ph2PCH2PPh2NH)2]Cl (1), [ReN(OSiMe3)(Ph2PCH2PPh2NH)2]Cl (2) or [ReNCl2(PPh3)2] (3) were isolated and structurally characterized. The latter compound was also produced during a reaction of the rhenium(III) precursor [ReCl3(PPh3)2(CH3CN)] and Me3SiNPPh3. Nitrogen transfer from the phosphorus to the rhenium atoms and the formation of nitrido ligands were observed in all examples. All products of reactions with an excess of the potentially chelating phosphoraneiminate Me3SiNP(Ph2)CH2PPh2 contain neutral Ph2PCH2PPh2NH ligands. The required protons are supplied by a metal-induced decomposition of the solvent dichloromethane. The Re-N(imine) bond lengths (2.055-2.110 A) indicate single bonds, whereas the N-P bond with lengths between 1.596 A and 1.611 A reflect considerable double bond character. An oxorhenium(V) phosphoraneiminato complex, the dimeric compound [ReOCl2(mu-N-Ph2PCH2PPh2N)]2 (4), is formed during the reaction of [NBu4][ReOCl4] with an equivalent amount of Ph2P(NSiMe3)CH2PPh in dry acetonitrile. The blue neutral complex with two bridging phosphoraneiminato units is stable as a solid and in dry solvents. It decomposes in solution, when traces of water are present. The rhenium-nitrogen distances of 2.028(3) and 2.082(3) A are in the typical range of bridging phosphoraneiminates and an almost symmetric bonding mode. Technetium complexes with phosphoraneimine ligands were isolated from reactions of [NBu4][TcOCl4] with Me3SiNPPh3, and [NBu4][TcNCl4] with Me3SiNP(Ph2)CH2PPh2. Nitrogen transfer and the formation of a five-coordinate nitrido species, [TcNCl2(HNPPh3)2] (5), was observed in the case of the oxo precursor, whereas reduction of the technetium(VI) starting material and the formation of the neutral technetium(V) complex [TcNCl2(Ph2PCH2PPh2NH)] (6) or [TcNCl(Ph2PCH2PPh2NH)2]Cl (7) was observed in the latter case. Both technetium complexes are air stable and X-ray structure determinations show bonding modes of the phosphoraneimines similar to those in the rhenium complexes.     

Direct determination of bismuth(III) in sea water by square-wave anodic stripping voltammetry at a glassy-carbon rotating-disk electrode

A method for the determination of bismuth(III) in untreated sea water at its natural pH of 8.1 is described. A bare glassy-carbon rotating-disk electrode is preconditioned by placing in the sample at an applied potential of ?0.8 V vs. Ag/AgCl for 20 min; after stripping to ?0.4 V, bismuth is accumulated for 5 min at ?0.8 V and finally stripped in the square-wave mode. The bismuth peak appears at ca. + 0.10 V vs. Ag/AgCl; peak height is linearly related to concentration up to 2×10^?10 mol dm^?3. The method is highly selective for bismuth. The concentration of Bi(III) in the investigated sample was (6±1)×10^?11 mol dm^?3, or 12±2 ng dm^?3. The different types of response obtained are discussed.     

Use of sulphide precipitation in separation and determination of molybdenum(V)

Molybdenum(V) is quantitatively precipitated as sulphide (99.7%) from 0.1 M At hydrochloric acid without formation of molybdenum blue and without need for a long digestion. Precipitation is more complete and co-precipitation less than with Mo(VI) sulphide. The precipitate can also be used directly for gravimetric estimation. In the presence of EDTA, molybdenum(V) sulphide is not precipitated from 0.1 M hydrochloric acid and can be separated from copper, bismuth, antimony and tin sulphides and determined cerimetrically in presence of the EDTA.     

Tetrachloroantimon(V)-methansulfinat

Tetrachloroantimony(V) Methanesulfinate Tetrachloroantimony(V) methanesulfinate II can be prepared by reaction of methanesulfinic acid chloride with the 1:1 addition compound of antimony(V) chloride and water resp. by reaction of sodium methanesulfinate with antimony(V) chloride. The mass spectrum shows that II is dimer. The mass and vibrational spectra are discussed.