A Redox‐Confused Bismuth(I/III) Triamide with a T‐Shaped Planar Ground State

Reaction of a tethered triamine ligand with Bi(NMe₂)₃ gives a Bi triamide, for which a Bi^I electronic structure is shown to be most appropriate. The T‐shaped geometry at bismuth provides the first structural model for edge inversion in bismuthines and the only example of a planar geometry for pnictogen triamides. Analogous phosphorus compounds exhibit a distorted pyramidal geometry because of different Bi?N and P?N bond polarities. Although considerable Bi^I character is indicated for the title Bi triamide, it exhibits reactivity similar to Bi^III electrophiles, and expresses either a vacant or a filled p orbital at Bi, as evidenced by coordination of either pyridine N‐oxide or W(CO)₅. The product of the former shows evidence of coordination‐induced oxidation state change at bismuth.     

Molecular Bismuth Cations: Assessment of Soft Lewis Acidity

Three-coordinate cationic bismuth compounds [Bi(diaryl)(EPMe₃)][SbF₆] have been isolated and fully characterized (diaryl=[(C₆H₄)₂C₂H₂]²⁻, E=S, Se). They represent rare examples of molecular complexes with Bi⋅⋅⋅EPR₃ interactions (R=monoanionic substituent). The ³¹P NMR chemical shift of EPMe₃ has been found to be sensitive to the formation of LA⋅⋅⋅EPMe₃ Lewis acid/base interactions (LA=Lewis acid). This corresponds to a modification of the Gutmann–Beckett method and reveals information about the hardness/softness of the Lewis acid under investigation. A series of organobismuth compounds, bismuth halides, and cationic bismuth species have been investigated with this approach and compared to traditional group 13 and cationic group 14 Lewis acids. Especially cationic bismuth species have been shown to be potent soft Lewis acids that may prefer Lewis pair formation with a soft (S/Se-based) rather than a hard (O/N-based) donor. Analytical techniques applied in this work include (heteronuclear) NMR spectroscopy, single-crystal X-ray diffraction analysis, and DFT calculations.     

Isolation and Characterization of a Bismuth(II) Radical

More than 80 years after Paneth’s report of dimethyl bismuth, the first monomeric Bi^II radical that is stable in the solid state has been isolated and characterized. Reduction of the diamidobismuth(III) chloride Bi(NON^Ar)Cl (NON^Ar=[O(SiMe₂NAr)₂]²⁻; Ar=2,6‐iPr₂C₆H₃) with magnesium affords the Bi^II radical ^.Bi(NON^Ar). X‐ray crystallographic measurements are consistent with a two‐coordinate bismuth in the +2 oxidation state with no short intermolecular contacts, and solid‐state SQUID magnetic measurements indicate a paramagnetic compound with a single unpaired electron. EPR and density functional calculations show a metal‐centered radical with >90 % spin density in a p‐type orbital on bismuth.     

Synthese und Kristallstrukturen der Bismutchalkogenolate Bi(SC6H5)3, Bi(SeC6H5)3 und Bi(S‐4‐CH3C6H4)3

Synthesis and Crystal Structures of Bismuth Chalcogenolato Compounds Bi(SC₆H₅)₃, Bi(SeC₆H₅)₃, and Bi(S‐4‐CH₃C₆H₄)₃ Bismuth(III) acetate reacts with thiophenol in ethyl alcohol at 80 °C to yield Bi(SC₆H₅)₃ ( 1 ). Slow cool down of the deep yellow mixture lead to the formation of orange crystals of 1 . The homotype phenylselenolato compound of bismuth Bi(SeC₆H₅)₃ ( 2 ) has been prepared by the reaction of BiX₃ (X = Cl, Br) with Se(C₆H₅)SiMe₃ in diethyl ether. In the same way as Bi(SC₆H₅)₃ ( 1 ) the reaction between bismuth(III) acetate and 4‐tolulenethiole results in red crystals of Bi(S‐4‐CH₃C₆H₄)₃ ( 3 ). In consideration of three longer Bi–E distances (intermolecular interactions, E = S; Se) the Bi(EPh)₃ molecules form via face‐linked octahedra 1‐dimensional chains in the crystal lattice, while for 3 the 1‐dimensional chain is formed by face‐linked trigonal prisma. We reported herein the synthesis and structures of Bi(SC₆H₅)₃ ( 1 ), Bi(SeC₆H₅)₃ ( 2 ), and Bi(S‐4‐CH₃C₆H₄)₃ ( 3 ).     

Synthesis and Characterization of Three Homoleptic Bismuth Silanolates: [Bi(OSiR3)3] (R = Me,Et, iPr)

The bismuth tris(triorganosilanolates) [Bi(OSiR₃)₃] ( 1 , R = Me; 2 , R = Et; 3 , R = iPr) were prepared by reaction of R₃SiOH with [Bi(OtBu)₃]. Compound 1 crystallizes in the triclinic space group with Z = 2 and the lattice constants a = 10.323(1) Å, b = 13.805(1) Å, c = 21.096(1) Å and α = 91.871(4)°, β = 94.639(3)°, γ = 110.802(3)°. In the solid state compound 1 is a trimer as result of weak intermolecular bismuth‐oxygen interactions with Bi–O distances in the range 2.686(6)–3.227(3) Å. The coordination at the bismuth atoms Bi(1) and Bi(3) is best described as 3 + 2 coordination whereas Bi(2) shows a 3 + 3 coordination. The intramolecular Bi–O distances fall in the range 2.041(3)–2.119(3) Å. Compound 3 crystallizes in the orthorhombic space group Pbcm with Z = 4 and the lattice constants a = 7.201(1) Å, b = 23.367(5) Å and c = 20.893(1) Å, whereas the triethylsilyl‐derivative 2 is liquid. In contrast to [Bi(OSiMe₃)₃] ( 1 ) compound 3 is monomeric in the solid state, but shows similar intramolecular Bi–O distances in the range 1.998(2)–2.065(5) Å. The bismuth silanolates are highly soluble in common organic solvents and strongly moisture sensitive. Compound 1 shows the lowest thermal stability.     

Bismuth Interfacial Doping of Organic Small Molecules for High Performance n‐type Thermoelectric Materials

Development of chemically doped high performance n‐type organic thermoelectric (TE) materials is of vital importance for flexible power generating applications. For the first time, bismuth (Bi) n‐type chemical doping of organic semiconductors is described, enabling high performance TE materials. The Bi interfacial doping of thiophene‐diketopyrrolopyrrole‐based quinoidal (TDPPQ) molecules endows the film with a balanced electrical conductivity of 3.3 S cm^?1 and a Seebeck coefficient of 585 μV K^?1. The newly developed TE material possesses a maximum power factor of 113 μW m^?1 K^?2, which is at the forefront for organic small molecule‐based n‐type TE materials. These studies reveal that fine‐tuning of the heavy metal doping of organic semiconductors opens up a new strategy for exploring high performance organic TE materials.     

Elektrochemische Synthese von Perowskiten im System K/Ba/Pr/Bi/O

Electrochemical Synthesis of Perovskites in the System K/Ba/Pr/Bi/O An easy procedure for the synthesis of well crystalline samples of (K,Ba)(Pr,Bi)O₃ is provided by anodic oxidation of melts consisting of Ba(OH)₂ / KOH / Pr(NO₃)₃ / Bi(NO₃)₃, at comparatively low temperatures of about 220 °C. We have explored the influence of different parameters like temperature, potential of the working electrode, and composition of the electrolyte. Chemical and thermal analyses were performed. Products obtained at different experimental conditions revealed different Ba/K and Pr/Bi ratios with a large homogeneity range. X‐Ray powder diffraction and single crystal structure analyses of K_xBa_1?xPr_yBi_1?yO₃ proved these compounds to be cubic perovskites. Barium and potassium ions are disordered occupying the A‐sites while praseodym and bismuth ions share the B‐sites or are ordered, as indicated by a doubling of the lattice parameter. The composition x and y can independently be altered. XPS analysis and physical properties are reported and discussed.     

铋(Ⅲ)配合物Bi(1,10-phen)[S2CN(CH3)2]2(NO3),

Three bismuth（Ⅲ） complexes Bi（1,10-phen）[S2CN（CH3）2]2（NO3） （1）, {Bi（S2COCH3）[S2CNC6Hs（CH3）]2}2 （2） and [Bi（S2CNBu2）2（CH3OH）（NO3）]∞ （3） were synthesized and characterized by elemental analysis and IR spectra. Their crystal structures were determined by X-ray single crystal diffraction analysis. Studies show that complex 1 has a monomeric structure with the central bismuth atom eight-coordinated in a capped distorted pentagonal bipyramidal geometry. The complex 2 takes centrosymmetric dimeric structure and the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry.In complex 3, the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry by bridging nitrate O atoms and the resulting structure is onedimensional infinite chain polymer.     

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.     

Structures of Bismuth(III) Complexonates in Aqueous Solutions Studied by 1H NMR Method

Aqueous solutions of bismuth(III) nitrilotriacetates BiNta · 2H₂O and M₃Bi(Nta)₂ ·nH₂O (M = Na, K, Rb, Cs, NH₄, CN₃H₆, n = 0–4) and the K[Bi(Edta)(Tu)₂] complex (Edta^4– is the anion of ethylenediaminetetraacetic acid, Tu is thiocarbamide) are studied by the ¹H NMR method at room temperature in the pH interval from 2 to 11. The formation of two types of bismuth nitrilotriacetate complexes in solutions is established. They are characterized by the presence (type 1) or absence (type 2) of the Bi–N bond. Their ratio, depending on the composition and pH of the solution, is determined. The K[Bi(Edta)(Tu)₂] compound in solutions occurs as one form. The pH values at which the substance begins to decompose are determined for each compound.     

Neutral and Cationic β‐Ketoiminato Bismuth Complexes

The first examples of neutral and cationic bismuth complexes bearing β‐ketoiminato ligands were isolated by employing salt metathesis route. BiCl₃ reacts with [O=C(Me)]CH[C(Me)N(K)Ar] ( 1 ) resulting in a homoleptic β‐ketoiminato bismuth complex Bi[{O=C(Me)}CH{C(Me)NAr}]₃ ( 2 ). The reaction between BiCl₃ and [(CH₂)₂{N(K)C(Me)CHC(Me)=O}₂] ( 3 ) leads to the formation of a cationic bismuth complex [Bi{(CH₂)₂(NC(Me)CHC(Me)=O)₂}]₄[Bi₂Cl₁₀] ( 4 ).     

[Bi(OSitBuPh2)3]: A Metal Silanolate with a Weak Bismuth ‐ π Arene Interaction

The title compound [Bi(OSitBuPh₂)₃] ( 1 ) was prepared by the reaction of [Bi(OtBu)₃] with tBuPh₂SiOH in toluene at room temperature. The compound crystallizes in the monoclinic space group P2₁/n with the lattice constants a = 17.610(1), b = 20.153(1), c = 26.655(1) Å and β = 105.503(3)°. In the solid state a dimer is observed as a result of weak bismuth π‐arene interactions. The bismuth arene centroid distance amounts to 3.340(7) Å. Thermolysis of compound 1 performed under argon gave a heterogeneous product. The powder X‐ray diffraction analysis of the latter shows elementary bismuth as the only crystalline phase.     

[Bi4]6– – The Zintl Anion with the Highest Charge per Atom Obtained from Solution

From the dark‐purple solution of the Zintl phase KBi in liquid ammonia dark‐blue crystals of the ammonia solvate K₆[Bi₄](NH₃)₈ were obtained. In contrast to known Bi_n polyanions the chemical bond in the anion [Bi₄]^6– is in accordance with the (8‐N) rule featuring solely Bi–Bi single bonds. [Bi₄]^6– is a butane‐analog valence compound, and with 6 negative charges per 4 atoms it is the anion with the highest known charge per atom obtained from solution. The planarity of the trans‐[Bi₄]^6– unit hints at π orbital contributions of the bismuth atoms. The corresponding reactions of the phases K₅Bi₄ and K₃Bi₂ in liquid ammonia in the presence of [2.2.2]crypt(4, 7, 13, 16, 21, 24‐hexaoxa‐1, 10‐diazabicyclo‐[8.8.8]hexacosane) lead to the salt [K([2.2.2]crypt)]₂[Bi₂](NH₃)₄ with the known electron‐deficient [Bi₂]^2– polyanion and a Bi=Bi double bond.     

Synthesis and structures of the first bismuth-ester complexes using heterobifunctional thiolate anchored ligands and mass spectrometric identification of ligand-bridged derivatives

The first systematic series of bismuth complexes involving ester donors, Bi(SCH(2)C(O)OCH(2)CH(3))Cl(2), Bi(SCH(2)C(O)OCH(3))(2)Cl, and Bi(SCH(2)COOCH(3))(3), has been isolated and characterized by spectroscopic (IR, Raman) and X-ray crystallographic data. In addition, these and other species have been identified by electron-impact, electrospray, and atmospheric pressure chemical ionization mass spectometry. The generally applicable synthetic methodology involves the use of heterobifunctional ligands containing a thiolate moiety as an anchor to facilitate coordinate interactions between weak donors (carbonyls) and weak acids (bismuth). The bifunctional nature of the ligands is manifested in both chelating and bridging roles. Important comparisons can be made with the pharmaceutical agent "colloidal bismuth subcitrate" (CBS). The observations allow for a new appreciation of bioactive bismuth compounds, by providing an approach to study the interaction of biorelevant functional groups with bismuth.     

Bismuth(III) dication trapped on a chlorobismuthate

Abstract

Metal cations observed with tetrachloroaluminate anion provide insights into the structure and stability of reactive cations. Addition of tris(3,5-dimethylpyrazolyl)borate anion (Tp^Me2) to [BiCl₂][AlCl₄] traps a bismuth(III) dication, [Tp^Me2Bi]²⁺, possessing a highly electrophilic bismuth center with short coordinate Bi―N bonds. [Tp^Me2Bi]²⁺ has weak interactions with the chlorides of [Bi₃Cl₁₃]_∞. Strong affinity of [Tp^Me2Bi]²⁺ with the triflate (OTf) observed in [Tp^Me2Bi(OTf)₃]^- demonstrates the high electrophilicity at bismuth.     

Dispersion interactions between neighboring Bi atoms in (BiH3)2 and Te(BiR2)2

Triggered by the observation of a short Bi⋯Bi distance and a Bi Te Bi bond angle of only 86.6° in the crystal structure of bis(diethylbismuthanyl)tellurane quantum chemical computations on interactions between neighboring Bi atoms in Te(BiR₂)₂ molecules (R = H, Me, Et) and in (BiH₃)₂ were undertaken. Bi⋯Bi distances atoms were found to significantly shorten upon inclusion of the d shells of the heavy metal atoms into the electron correlation treatment, and it was confirmed that interaction energies from spin component‐scaled second‐order Møller–Plesset theory (SCS‐MP2) agree well with coupled‐cluster singles and doubles theory including perturbative triples (CCSD(T)). Density functional theory‐based symmetry‐adapted perturbation theory (DFT‐SAPT) was used to study the anisotropy of the interplay of dispersion attraction and steric repulsion between the Bi atoms. Finally, geometries and relative stabilities of syn–syn and syn–anti conformers of Te(BiR₂)₂ (R = H, Me, Et) and interconversion barriers between them were computed. © 2018 Wiley Periodicals, Inc.     

Studies on the thermal decomposition of alkali metal thiosulphatobismuthates(III)

The thermal decomposition of thiosulphatobismuthates(III) of alkali metals was investigated. The general formulae of the thiosulphatobismuthates are M₃[Bi(S₂O₃)₃]·H₂O where M = Na, K, Rb or Cs, and M₂Na[Bi(S₂O₃)₃]·H₂O where M = K or Cs.Typical thermal curves for thiosulphatobismuthates(III) and the results obtained in thermal, X-ray, chemical and spectrophotometrical analyses of the decomposition products are shown. The results were used to determine three stages of the thermal decomposition. At the first stage, at about 200°C, hydrated compounds are dehydrated. At the second stage, above 200°C, there is a rapid decrease in mass which is caused by evolving sulphur dioxide; bismuth sulphide and an intermediate decomposition product are formed. At about 320°C the thermal decomposition products are bismuth sulphide and alkali metal sulphate.     

Differential Pulse Anodic Stripping Voltammetric Determination of Bismuth(III) with 1‐(2‐Pyridylazo)‐2‐naphthol and Ionic Liquid Modified Carbon Paste Electrode

In this paper 1‐(2‐pyridylazo)‐2‐naphthol (PAN) and ionic liquid 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF₄) were mixed with graphite powder to get a modified carbon paste electrode (PAN‐IL‐CPE), which was further used for the sensitive determination of bismuth(III). By the co‐contribution of the formation of PAN‐Bi complex and the accumulation effect of IL, more bismuth(III) was electrodeposited on the surface of the PAN‐IL‐CPE. Then the reduced Bi was oxidized and detected by differential pulse anodic stripping voltammetry (DPASV) with the oxidation peak appeared at 0.17 V (vs. SCE). Under the optimal conditions the oxidation peak current was proportional to the bismuth(III) concentration in the range from 0.04 to 7.5 μmol L^?1 with the detection limit as 3.9 nmol L^?1. The proposed method was successfully applied to the stomach medicine sample detection with good recovery.     

Bismuth(III) dimethyldithioarsinate,Bi(S2AsMe2)3: A new dimer formed through Bi … S secondary bonding

The crystal and molecular structures of bismuth(III) dimethyldithioarsinate, Bi(S₂AsMe₂)₂, were investigated by X-ray diffraction. The compound is a centrosymmetric dimer in which pentagonal-bipyramidal monomeric units are associated through secondary Bi–S interactions. The structure is compared with that of the analogous dithiophosphinate, Bi(S₂PMe₂)₂. © 1997 John Wiley & Sons, Inc.     

A new bismuth iron oxyphosphate,Bi6(Bi0.32Fe0.68)(PO4)4O4

Iron was inserted into the known crystal structure of the bismuth phosphate oxide Bi_6.67(PO₄)₄O₄ to ascertain its location in the vacancies associated with the bismuth ion located at the origin of the unit cell. Single‐crystal X‐ray diffraction refinements converged to a model of composition Bi₆(Bi_0.32Fe_0.68)(PO₄)₄O₄ (hexabismuth iron tetraphosphate tetraoxide), in which Bi and Fe are displaced from the origin giving rise to a random distribution over the 2i sites instead of 1a, the origin of space group P. The isotropic displacement parameter for Bi/Fe has a reasonable value in this model. This structure establishes for the first time that Fe substitutes in the Bi‐deficient site in this series of materials and that Fe and Bi are disordered around the center of symmetry. These results enhance understanding of the crystal chemistry of these main group phosphates that are of interest in ion transport.