- Phenylbismuth bis(2,5-dimethylbenzenesulfonate): Structure and properties
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Phenylbismuth bis(2,5-dimethylbenzenesulfonate) (I), a coordination polymer in which a bis-muth atom has a distorted square pyramidal coordination to an axial carbon atom (Bi-C, 2.247(5) A?) and basal oxygen atoms (Bi-O, 2.390(9)-2.403(10) A?), has been synthesized by the reaction between triphenyl- bismuth and 2,5-dimethylbenzenesulfonic acid (1 : 2 mol/mol) in toluene and structurally characterized. Pentaphenylbismuth and pentaphenylantimony phenylate compound I to triphenylbismuth.
- Sharutin,Sharutina
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- Oxidation of magnesium with diphenylbismuth and diphenylantimony chlorides in polar solvents
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The intermediate and final products of the reactions of magnesium with diphenylantimony and diphenylbismuth chlorides were identified, and the formal kinetic relationships of the process were elucidated. The apparent equilibrium constants, enthalpies, and
- Maslennikov,Klement'eva,Losev, Ya. V.,Spirina,Maslennikov
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- Making Bispirin: Synthesis, structure and activity against Helicobacter pylori of bismuth(iii) acetylsalicylate
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Reaction of Bi(OtBu)3 with aspirin (acetylsalicylic acid = aspH) in dry toluene results in the bismuth(iii) complex, [Bi(O 2C(C6H4)OAc)3]∞ 1 (O2C(C6H4)OAc = asp), minimum inhibitory concentration (MIC) against Helicobacter pylori ≥ 6.25 μg mL-1, while the inclusion of a stoichiometric equivalent of KOtBu leads to crystals of the bismuthate salt [KBi(O2C(C6H 4)OAc)4]∞ 2. The Royal Society of Chemistry 2013.
- Andrews, Philip C.,Blair, Victoria L.,Ferrero, Richard L.,Junk, Peter C.,Kumar, Ish
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- Reactivity of TerN(SiMe3)BiCl2 - Synthesis of an Aminobismuthenium Cation and TerN(SiMe3)Bi(N3)2
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The reaction of TerN(SiMe3)BiCl2 (1) (Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl) with Lewis acids such as GaCl3 and Ag[OTf] (OTf = OSO2CF3) was studied. While the reaction of 1 with GaCl3 led to decomposition into bismuth black, TerNH2·GaCl3, and [TerNH3][GaCl4], the reactions of 1 with 1 and 2 equiv of Ag[OTf] resulted in methyl/triflate exchange reactions affording TerN(SiMe2OTf)Bi(Me)Cl (2) and TerN(SiMe2OTf)Bi(Me)OTf (3). To circumvent the methyl/triflate exchange, the diiodide compound TerN(SiMe3)BiI2 (5) and the azide-substituted derivatives TerN(SiMe3)Bi(Cl)N3 (6) and TerN(SiMe3)Bi(N3)2 (7) were prepared, although it was not possible to isolate pure 7 because of small impurities of 6. All of the bismuth compounds (1-7) were characterized by single-crystal X-ray diffraction and NMR, IR, and Raman spectroscopy. According to quantum-chemical calculations, 3 can be regarded as a donor-stabilized aminobismuthenium cation with OTf- as the counterion. As expected for bismuth compounds with aromatic scaffolds, Bi···-arene interactions were observed. The influence of the substitution at the bismuth atom on the strength of this intramolecular interaction with the terphenyl moiety was studied by experimental (crystal structures) and theoretical methods. A correlation between the Lewis acidity (NBO charge) and the Bi···-arene distance could be established.
- Bresien, Jonas,Hering-Junghans, Christian,Schulz, Axel,Thomas, Max,Villinger, Alexander
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- Bismuth(III) saccharinate and thiosaccharinate complexes and the effect of ligand substitution on their activity against helicobacter pylori
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Five bismuth(III) saccharinate and thiosaccharinate complexes, [Ph 2Bi(sac)]∞1, [Bi(sac)3]n2, [Ph2Bi(tsac)]∞4, [PhBi(tsac)2] n5, [Bi(tsac)3]n6 (sacH = saccharin, tsacH = thiosaccharin), have been synthesized and fully characterized. The tendency for ligand redistribution in [Ph2Bi(sac)]∞ has been investigated in solution by NMR spectroscopy. The structures of [Ph 2Bi(sac)]∞1 and [Ph2Bi(tsac)] ∞4 have been confirmed by X-ray crystallography. In Ph 2Bi(sac) the sac ligand is bound to a four-coordinate bismuth center via its imino nitrogen atom with an accompanying long-range Bi-O interaction. However, in the structure of [Ph2Bi(tsac)]∞ the ligand is σ-bound through the exocyclic sulfur atom, giving a thiolate complex, confirming the more thiophilic nature of bismuth(III). Both complexes consist of polymeric chain structures with formally four-coordinated bismuth atoms. The complexes were assessed for their activity against H. pylori. The activity is both ligand dependent and sensitive to the degree of ligand substitution. The saccharinate complexes, 1 and 2, show activity comparable with standard tris-carboxylato bismuth(III) compounds, 6.25 μg/mL, while the activity of the thiolato complexes, 4-6, increases dramatically on increasing the number of thiolate groups from one to three (range 50-6.25 μg/mL). Saccharin, thiosaccharin, and BiPh3 were found to be inactive.
- Andrews, Philip C.,Ferrero, Richard L.,Forsyth, Craig M.,Junk, Peter C.,MacLellan, Jonathan G.,Peiris, Roshani M.
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- Zinc reaction with diphenylantimony and diphenylbismuth chlorides in aprotic solvents
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Products of zinc oxidation with diphenylantimony and diphenylbismuth chlorides in aprotic solvents are established. The effective adsorption constants of the reagents on the metal surface and the rate constants and activation energies of the processes und
- Losev,Klement'eva,Maslennikov,Spirina
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- The Importance of Heterolepticity in Improving the Antibacterial Activity of Bismuth(III) Thiolates
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Five mixed thiolatobismuth(III) complexes [BiPh(5-MMTD)2{4-MMT(H)}] (1), [Bi(1-MMTZ)2{(PYM)(PYM(H))2}] (2), [Bi(MBT)2(5-MMTD)] (3), [Bi(4-BrMTD)3{2-MMI(H)}] (4) and [Bi(1-MMTZ)2{1-MMTZ(H)}(
- Luqman, Ahmad,Blair, Victoria L.,Brammananth, Rajini,Crellin, Paul K.,Coppel, Ross L.,Andrews, Philip C.
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- Formation of bismuth(V) thiolates: Protolysis and oxidation of triphenylbismuth(III) with heterocyclic thiols
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Stressing bismuth: Two monophenyl tetrathiolato BiV complexes, [BiPh(SR)4], have been prepared upon treating BiPh3 in toluene/ethanol under reflux conditions with an excess of N-heterocyclic thiols (see scheme), indicating
- Luqman, Ahmad,Blair, Victoria L.,Bond, Alan M.,Andrews, Philip C.
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- Homoleptic and heteroleptic bismuth(III) thiazole-thiolates and the influence of ring substitution on their antibacterial and antileishmanial activity
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Two new homo- and heteroleptic bismuth thiazole-thiolato complexes derived from 4-phenylthiazole-2-thiol MBT(H) have been synthesised and structurally characterised, [BiPh(MBT)2]2 and [Bi(MBT)3]2. Syntheses were achieved using BiPh3 or Bi(OtBu)3 in protolysis reactions with MBT(H), or by salt metathesis with BiCl3 or BiPhCl2 and the sodium thiolate, [NaMBT]. The complexes were obtained under both standard solvent-free and solvent-mediated conditions, and by microwave irradiation. The solid-state structures of [BiPh(MBT)2]2 and [Bi(MBT)3]2, were determined using single-crystal X-ray diffraction, showing them to be dimeric. The bactericidal properties of the complexes against Mycobacterium smegmatis, Staphylococcus aureus, methicillin-resistant Staphylococcus aureus (MRSA), Enterococcus faecalis, vancomycin-resistant Enterococcus (VRE) and Escherichia coli revealed [BiPh(MBT)2]2 to be the most effective against all the bacteria with MIC values of 0.6 μg/mL (0.25 μM) against S. aureus and 0.9 μg/mL (0.27 μM) against E. faecalis. [Bi(MBT)3]2 was less active overall. However, comparisons with the analogous complex [Bi(4-BrMTD)3], revealed a significant hundred-fold enhanced activity against S. aureus, MRSA, VRE, and E. faecalis. Both complexes showed little or no toxicity towards mammalian COS-7 cells at 20 μg/mL. [BiPh(MBT)2]2 also was found to display good antileishmanial activity with an IC50 value of 0.11 μg/mL (0.17 μM), at which concentration the complex was non-toxic to human fibroblast cells.
- Luqman, Ahmad,Blair, Victoria L.,Brammananth, Rajini,Crellin, Paul K.,Coppel, Ross L.,Kedzierski, Lukasz,Andrews, Philip C.
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- The thiol-based reduction of Bi(V) and Sb(V) anti-leishmanial complexes
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Low molecular weight thiols including trypanothione and glutathione play an important function in the cellular growth, maintenance and reduction of oxidative stress in Leishmania species. In particular, parasite specific trypanothione has been established as a prime target for new anti-leishmania drugs. Previous studies into the interaction of the front-line Sb(V) based anti-leishmanial drug meglumine antimoniate with glutathione, have demonstrated that a reduction pathway may be responsible for its effective and selective nature. The new suite of organometallic complexes, of general formula [MAr3(O2CR)2] (M = Sb or Bi) have been shown to have potential as new selective drug candidates. However, their behaviour towards the critical thiols glutathione and trypanothione is still largely unknown. Using NMR spectroscopy and mass spectrometry we have examined the interaction of the analogous Sb(V) and Bi(V) organometallic complexes, [SbPh3(O2CCH2(C6H4CH3))2] S1 and [BiPh3(O2CCH2(C6H4CH3))2] B1, with the trifluoroacetate (TFA) salt of trypanothione and L-glutathione. In the presence of trypanothione or glutathione at the clinically relevant pH of 4–5 for Leishmania amastigotes, both complexes undergo facile and rapid reduction, with no discernible difference. However, at a higher pH (6–7), the complexes behave quite differently towards glutathione. The Bi(V) complex is again reduced rapidly but the Sb(V) complex undergoes slow reduction over 8 h (t1/2 = 54 min.) These results give the first insights into why the highly oxidising Bi(V) complexes display low selectivity in their cytotoxicity towards leishmanial and mammalian cells, while the Sb(V) complexes show good selectivity.
- Duffin, Rebekah N.,Stephens, Liam J.,Blair, Victoria L.,Kedzierski, Lukasz,Andrews, Philip C.
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- METHOD FOR PREPARING HETEROLEPTIC TRIARYLBISMUTHANES AND COMPOUNDS PRODUCED BY THE SAME
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A method for controlling dismutation in the synthesis of a heteroleptic triarylbismuthane is provided as are compounds produced by such a method and use of the same to inhibit the replication of microorganisms.
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Paragraph 0072
(2021/05/21)
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- Bismuth(iii) Thiophosphinates: Understanding How a Small Atomic Change Influences Antibacterial Activity and Mammalian Cell Viability
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Diphenylphosphinothioic acid (HSP(=O)Ph2) and diphenylphosphinodithioic acid (HSP(=S)Ph2) have been used to synthesise four BiIII complexes: 1 [Bi(SP(=O)Ph2)3], 2 [BiPh(SP(=O)Ph2)2], 3 [BiPh2(SP(=O)Ph2)], and 4 [Bi(SP(=S)Ph2)3], using BiPh3 and [Bi(OtBu)3] as bismuth sources. The complexes have been characterised by NMR spectroscopy, mass spectrometry, infrared spectroscopy, powder X-ray diffraction, and singe crystal X-ray crystallography (2-4). Biological studies indicated that despite complexes 2 and 3 reducing mammalian cell viability, their antibacterial activity provides a good degree of selectivity towards both Gram positive and Gram negative bacterial strains. The minimum inhibitory concentrations for complexes 2 and 3 are in the range of 0.52-5.5 μM towards the bacteria tested. Homoleptic complexes 1 and 4 were generally less active towards both bacterial and mammalian cells.
- Senevirathna, Dimuthu C.,Duffin, Rebekah N.,Stephens, Liam J.,Herdman, Megan E.,Werrett, Melissa V.,Andrews, Philip C.
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p. 1226 - 1236
(2020/10/07)
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- Investigation into the Organobismuth Dismutation and Its Use for Rational Synthesis of Heteroleptic Triarylbismuthanes, Ar12Ar2Bi
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Organobismuthanes undergo dismutation, a substituent scrambling process, complicating the synthesis of unsymmetrically trisubstituted bismuthanes of the general formula Ar12Ar2Bi. Although the dismutation is a mechanistically diverse phenomenon, at ambient or lower temperatures, dismutation is triggered mainly by an electrophilic bismuth source. Therefore, the selection of the electrophile, Ar12BiX (X = tosylate or iodide if Ar1 = mesityl) or Ar1BiX2 (X = tosylate), and its use in low concentration during the reaction is key to suppressing the dismutation, leading to new, streamlined protocols utilizing direct arylations of Ar12BiX (X = OTs or I) or Ar1Bi(OTs)2 with organozincs affording heteroleptic triarylbismuthanes Ar12Ar2Bi.
- Hyvl, Jakub,Louis-Goff, Thomas,Rheingold, Arnold L.
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supporting information
(2020/03/16)
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- Bismuth Phosphinates in Bi-Nanocellulose Composites and their Efficacy towards Multi-Drug Resistant Bacteria
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A series of poorly soluble phenyl bis-phosphinato bismuth(III) complexes [BiPh(OP(=O)R1R2)2] (R1=R2=Ph; R1=R2=p-OMePh; R1=R2=m-NO2Ph; R1=Ph, R2=H; R1=R2=Me) have been synthesised and characterised, and shown to have effective antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Enterococcus (VRE). The bismuth complexes were incorporated into microfibrillated (nano-) cellulose generating a bismuth-cellulose composite as paper sheets. Antibacterial evaluation indicates that the Bi-cellulose materials have analogous or greater activity against Gram positive bacteria when compared with commercial silver based additives: silver sulfadiazine loaded at 0.43 wt % into nanocellulose produces a 10 mm zone of inhibition on the surface of agar plates containing S. aureus whereas [BiPh(OP(=O)Ph2)2] loaded at 0.34 wt % produces an 18 mm zone of inhibition. These phenyl bis-phosphinato bismuth(III) complexes show potential to be applied in materials in healthcare facilities, to inhibit the growth of bacteria capable of causing serious disease.
- Werrett, Melissa V.,Herdman, Megan E.,Brammananth, Rajini,Garusinghe, Uthpala,Batchelor, Warren,Crellin, Paul K.,Coppel, Ross L.,Andrews, Philip C.
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p. 12938 - 12949
(2018/08/11)
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- Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds – an experimental and theoretical study
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The dispersion type Bi···π arene interaction is one of the important structural features in the assembly process of arylbismuth compounds. Several triarylbismuth compounds and polymorphs are discussed and compared based on the analysis of single crystal X-ray diffraction data and computational studies. First, the crystal structures of polymorphs of Ph3Bi (1) are described emphasizing on the description of London dispersion type bismuth···π arene interactions and other van der Waals interactions in the solid state and the effect of it on polymorphism. For comparison we have chosen the substituted arylbismuth compounds (C6H4-CHCH2-4)3Bi (2), (C6H4-OMe-4)3Bi (3), (C6H3-t-Bu2-3,5)3Bi (4) and (C6H3-t-Bu2-3,5)2BiCl (5). The structural analyses revealed that only two of them show London dispersion type bismuth···π arene interactions. One of them is the styryl derivative 2, for which two polymorphs were isolated. Polymorph 2a crystallizes in the orthorhombic space group P212121, while polymorph 2b exhibits the monoclinic space group P21/c. The general structure of 2a is similar to the monoclinic C2/c modification of Ph3Bi (1a), which leads to the formation of zig-zag Bi–arenecentroid ribbons formed as a result of bismuth···π arene interactions and π···π intermolecular contacts. In the crystal structures of the polymorph 2b as well as for 4 bismuth···π arene interactions are not observed, but both compounds revealed C–HPh···π intermolecular contacts, as likewise observed in all of the three described polymorphs of Ph3Bi. For compound 3 intermolecular contacts as a result of coordination of the methoxy group to neighboring bismuth atoms are observed overruling Bi···π arene contacts. Compound 5 shows a combination of donor acceptor Bi···Cl and Bi···π arene interactions, resulting in an intermolecular pincer-type coordination at the bismuth atom. A detailed analysis of three polymorphs of Ph3Bi (1), which were chosen as model systems, at the DFT-D level of theory supported by DLPNO-CCSD(T) calculations reveals how van der Waals interactions between different structural features balance in order to stabilize molecular arrangements present in the crystal structure. Furthermore, the computational results allow to group this class of compounds into the range of heavy main group element compounds which have been characterized as dispersion energy donors in previous work.
- Preda, Ana-Maria,Krasowska, Ma?gorzata,Wrobel, Lydia,Kitschke, Philipp,Andrews, Phil C.,MacLellan, Jonathan G.,Mertens, Lutz,Korb, Marcus,Rüffer, Tobias,Lang, Heinrich,Auer, Alexander A.,Mehring, Michael
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supporting information
p. 2125 - 2145
(2018/09/04)
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- Triphenylbismuth(v) di[(iso)nicotinates]-transmetallation agents or divergent organometalloligands? First organobismuth(v)-based silver(i) coordination polymers
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The reaction of Ph3BiCl2 with alkali salts of isonicotinic and nicotinic acids afforded Ph3Bi[O(O)CC5H4N-4]2 (1) and Ph3Bi[O(O)CC5H4N-3]2 (2), respectively, which were characterized by multinuclear NMR spectroscopy in solution, mass spectrometry and IR spectroscopy in the solid state. Their molecular structures were established by single-crystal X-ray diffraction. For both 1 and 2 the molecules contain a trigonal bipyramidal C3BiO2 core, with the phenyl groups in equatorial positions. The potential use of 1 and 2 as ditopic organometalloligands was investigated. The reaction of 1 or 2 with Me3SnCl (1:2 molar ratio) resulted in carboxylato ligand exchange and the formation of Me3Sn[O(O)CC5H4N-4] (3) and Me3Sn[O(O)CC5H4N-3] (4) besides Ph3BiCl2. The crystals of both 3 and 4 contain 1-D coordination polymers built through intermolecular N → Sn interactions. The treatment of Ni[S2P(OiPr)2]2 with 1 and 2, respectively, resulted, in addition to di(carboxylato)nickel(ii) derivatives, in isolation of Ph3Bi and the disulphane [(iPrO)2P(S)S]2. New coordination polymers were obtained by reacting 1 and 2 with various silver(i) salts: [Ag{Ph3Bi[O(O)CC5H4N-4]2}(OTf)] (5), [Ag{Ph3Bi[O(O)CC5H4N-3]2}(OTf)]·CH2Cl2 (6·CH2Cl2), [Ag{Ph3Bi[O(O)CC5H4N-4]2}](SbF6)·2THF (7·2THF), [Ag{Ph3Bi[O(O)CC5H4N-3]2}](SbF6)·CH2Cl2 (8·CH2Cl2) and [Ag{Ph3Bi[O(O)CC5H4N-3]2}(NO3)]·CH2Cl2 (9·CH2Cl2). The crystal structures of 5 and 6 can be described as 1-D chains linked by triflate bridges in pairs of chains and 2-D networks, respectively. Compound 7 features a 2-D grid-like topology of the network, with tecton 1 acting as a tridentate ligand through both nitrogen and one oxygen atoms. The linker 2 molecules adopt either cis (compound 6) or trans (compounds 8 and 9) conformation. Complexes 8 and 9 are 1-D chain polymers exhibiting zig-zag and wavy motifs, respectively. The dimensionality of the structures is extended by the presence of supramolecular interactions (π?π, Ag?Ag, Ag?O).
- Ben Kiran, Ahmad,Mocanu, Teodora,P?llnitz, Alpár,Shova, Sergiu,Andruh, Marius,Silvestru, Cristian
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p. 2531 - 2542
(2018/02/28)
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- BISMUTH PERFLUOROALKYLPHOSPHINATES AS LEWIS ACID CATALYSTS
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The invention relates to bismuth perfluoroalkylphosphinates as Lewis acid catalysts, the compounds, and processes for the preparation thereof. [in-line-formulae]ArxBi[OP(O)(Rf)2]3-x??(Ia),[/in-line-formulae] [in-line-formulae]Ar3Bi[OP(O)(Rf)2]2??(Ib).[/in-line-formulae]
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Paragraph 0088; 0089; 0090; 0091
(2018/10/19)
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- Reversibly thermochromic bismuth-organic materials with tunable optical gaps
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Five reversibly thermochromic bismuth-based inorganic-organic hybrid materials were synthesized via facile one-step condensation reactions between triphenylbismuth and four arenedithiols and a diselenol. The materials were characterized by UV-vis and FT-IR spectroscopy, powder X-ray diffraction (PXRD), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), elemental analysis (EA), and thermogravimetric analysis (TGA). The bismuth-organic materials (Bi-OMs) are colored materials with optical HOMO-LUMO gaps that were readily tuned by systematic modification of the steric and electronic character of the π-conjugated organic linkers. All five Bi-OMs exhibit completely reversible thermochromism in the solid-state, and possess excellent thermal stability in air up to nearly 300 °C. This combination of physical properties, coupled with the ease of synthesis and the inexpensive, non-toxic nature of bismuth, make this class of inorganic-organic hybrid materials potentially promising for reversible smart window applications, camouflage coatings, temperature sensing, photocatalysis, color filters and displays.
- Zhang, Guoxian,Chan, Julian M. W.
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supporting information
p. 10007 - 10015
(2017/10/13)
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- Synthesis of highly functionalized triarylbismuthines by functional group manipulation and use in palladium- and copper-catalyzed arylation reactions
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Organobismuthines are an attractive class of organometallic reagents that can be accessed from inexpensive and nontoxic bismuth salts. Triarylbismuthines are particularly interesting due to their air and moisture stability and high functional group tolerance. We report herein a detailed study on the preparation of highly functionalized triarylbismuth reagents by triple functional group manipulation and their use in palladium- and copper-catalyzed C-, N-, and O-arylation reactions.
- Hébert, Martin,Petiot, Pauline,Benoit, Emeline,Dansereau, Julien,Ahmad, Tabinda,Le Roch, Adrien,Ottenwaelder, Xavier,Gagnon, Alexandre
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p. 5401 - 5416
(2016/07/13)
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- Powerful Antibacterial Activity of Phenyl-Thiolatobismuth(III) Complexes Derived from Oxadiazolethiones
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Seven novel 5-substituted phenylthiazole oxadiazolethiones: [Me-PTOT(H)], [MeO-PTOT(H)], [MeS-PTOT(H)], [F-PTOT(H)], [Cl-PTOT(H)], [Br-PTOT(H)], and [CF3-PTOT(H)], {where X-PTOT(H) = 5-[2-(4-X)thiazol-4-yl]-1,3,4-oxadiazole-2(3H)-thione, 4-X = C6H4}, were synthesised from their corresponding thioamides. From these seven heteroleptic thiolatobismuth complexes: BiPh(Me-PTOT)2 6, BiPh(MeO-PTOT)2 7, BiPh(MeS-PTOT)2 8, BiPh(F-PTOT)2 9, BiPh(Cl-PTOT)2 10, BiPh(Br-PTOT)2 11 and BiPh(CF3-PTOT)2 12 were synthesised and characterised. Complexes [10(DMSO)2] and [11(DMSO)2] were structurally characterised using X-ray diffraction. Evaluation of the antibacterial properties of the thiones and their BiIII complexes against Mycobacterium smegmatis, Staphylococcus aureus (S. aureus), Methicillin-resistant Staphylococcus aureus (MRSA), Vancomycin-resistant Enterococcus (VRE), Enterococcus faecalis (E. faecalis) and Escherichia coli (E. coli) showed that all bismuth(III) complexes were highly effective against all the bacteria, as demonstrated by very low MIC values (1.1-2.1 μM). Complexes BiPh(Me-PTOT)2 6, BiPh(Cl-PTOT)2 10 and BiPh(Br-PTOT)2 11, showed best activity against the multi-drug resistant bacteria VRE and MRSA with an MIC value of 1.0 μM. All these complexes and their corresponding thiones failed to show any prominent activity against M. smegmatis and E. coli, even at high concentrations. These complexes showed little or no toxicity towards mammalian COS-7 cells at 20 μg/mL. Seven heteroleptic thiolatobismuth(III) complexes [BiPh(X-PTOT)2] derived from a series of 5-substituted phenylthiazole oxadiazolethiones [X-PTOT(H)] provide powerful antibacterial action against the multi-resistant bacteria MRSA and VRE.
- Luqman, Ahmad,Blair, Victoria L.,Brammananth, Rajini,Crellin, Paul K.,Coppel, Ross L.,Andrews, Philip C.
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p. 4935 - 4945
(2015/11/02)
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- Homo- And heteroleptic bismuth(iii/v) thiolates from N-heterocyclic thiones: Synthesis, structure and anti-microbial activity
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Homo- and heteroleptic bismuth thiolato complexes have been synthesised and characterised from biolog,ically relevant tetrazole-, imidazole-, thiadiazole- and thia-zole- based heterocyclic thiones (thiols): 1-methyl-1 H-tetra-zole- 5-thiol (1-MMTZ(H)); 4-
- Luqman, Ahmad,Blair, Victoria L.,Andrews, Philip C.,Brammananth, Rajini,Crellin, Paul K.,Coppel, Ross L.
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p. 14362 - 14377
(2015/04/14)
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- A sweeter way to combat Helicobacter pylori? Bismuth(III) complexes and oxido-clusters derived from non-nutritive sweeteners and their activity against H. pylori
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Eight new homo-and hetero-leptic bismuth(III) complexes and two new polynuclear bismuth(III) oxido clusters derived from acetosulfame (AceH) and cyclamic acid (CycH2) have been synthesised and characterised. Complexes, [Ph2Bi(Ace)] 1, [Bi(Ace)3] 2, [PhBi(Ace)2] 3, [Bi(CycH)3] 6, [Ph2Bi(CycH)] 7 and [PhBi(CycH) 2] 8 were synthesised by treating BiPh3 with the appropriate acid in 1:1, 1:2 and 1:3 stoichiometric ratios under solvent-free or solvent-mediated conditions. Complex 4, [Bi(OH)(Ace)2], was obtained from the hydrolysis of 3. [Bi2(Cyc)3] 9 was obtained from the reaction of cyclamic acid with (Bi(OtBu)3) in a 3:2 ratio under inert conditions. The polynuclear bismuth oxido clusters, [Bi 50O64(Ace)22(H2O)10] 5 and [Bi38O45(CycH)24(H2O) 14] 10 were obtained using Bi2O3 under sonication in water and their composition confirmed through elemental and thermogravimetric analyses. The DMSO soluble complexes, 1, 2, 4, 5, 6, 7 and 9, were all assessed for their in-vitro activity against three strains of H. pylori (251, 26695 and B128). All compounds gave an MIC value of 6.25 μg/mL, indicating that bactericidal activity is insensitive to increased substitution by acetosulfamate or cyclamate at the Bi(III) centre.
- Andrews, Philip C.,Ferrero, Richard L.,Junk, Peter C.,Peiris, Roshani M.
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- Anti-leishmanial activity of novel homo- and heteroleptic bismuth(iii) thiocarboxylates
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Two new thiocarboxylic acids, p-bromothiobenzoic BTA and thionaphthoic acid TNA, and five new homo- and heteroleptic bismuth(iii) compounds derived from thiocarboxylic acids: [Bi{S(C≤O)C6H4Br}3] 1, [PhBi{S(C≤O)C6H4Br}2] 2, [Bi{S(C≤O)C10H7}3] 3, [PhBi{S(C≤O)C10H7}2] 4, and [Ph2Bi{S(C≤O)C10H7}] 5 were synthesised and fully characterised. The solid-state structure of complex [PhBi{S(C≤O)C6H4Br}2] 2 was confirmed by X-ray crystallography. In complex 2, the two thiocarboxylate ligands are coordinated to the bismuth(iii) centre in a didentate fashion, forming a distorted octahedral geometry in which the phenyl group and the lone pair are oriented axial to the plane formed by the two thiocarboxylate ligands. Long-range Bi-S interactions (3.54A) link these monomeric units to form a one-dimensional polymer. These compounds, in addition to six previously synthesised complexes: [Bi{SC(≤O)C6H5}3] 6, [PhBi{SC(≤O)C6H5}2] 7, [Ph2Bi{SC(≤O)C6H5}] 8, [Bi{SC(≤O)C6H4NO2}3] 9, [PhBi{SC(≤O)C6H4NO2}2] 10, and [PhBi{SC(≤O)C6H4SO3}] 11, and the thiocarboxylic acids themselves, were assessed for their in vitro activity against Leishmania major promastigotes, and for general toxicity against human fibroblast cells. The thiocarboxylic acids, with the exception of thiobenzoic acid and sulfothiobenzoic acid, were toxic to both L. major parasites and the mammalian cells at high concentrations of 50-100M. The bismuth(iii) thiocarboxylate derivatives proved to be more active than the corresponding acids. Among these, the heteroleptic phenyl-substituted bismuth(iii) complexes 2, 4, 5, and 7 were highly active, showing IC50 (half maximal inhibitory concentration) values ranging from 0.39 to 4.69M, and a clear ligand dependence on activity.
- Andrews, Philip C.,Junk, Peter C.,Kedzierski, Lukasz,Peiris, Roshani M.
-
p. 1297 - 1305
(2013/10/22)
-
- Structural and solution studies of phenylbismuth(III) sulfonate complexes and their activity against Helicobacter pylori
-
Three bis-phenylbismuth sulfonates [Ph2Bi(O3SR)] ∞ (R = p-tolyl 1, mesityl 2 or S-(+)-10-camphoryl 3) have been synthesised and characterised. Their tendency for ligand redistribution in solution, and activity against the bacterium Helicobacter pylori have been investigated. The structures of 2 and 3 have been authenticated by X-ray diffraction crystallography. They are structurally very similar with polymeric helical chain structures composed of four coordinate Bi atoms which bridge between two sulfonate O atoms with near linear O-Bi-O bond angles. The two phenyl rings are cis to one another and trans to the stereochemically active lone pair. Upon dissolution of the pure compounds 1, 2 and 3, a ligand redistribution reaction occurs in which the mono-phenylbismuth bis-sulfonates, the bismuth tris-sulfonates and triphenylbismuth are formed. Two further complexes of general formula [PhBi(O3SR)2] ∞ (where R = p-tolyl 4, and mesityl 5) were thus obtained and their crystal structures determined. The presence of the single sulfonato ligand in compounds 1, 2 and 3 resulted in a dramatic increase in bacteriocidial activity towards H. pylori (MIC values of ≥6.25 μg mL-1) relative to BiPh3 (>64 μg mL-1) and the sulfonic acids, which were essentially inactive.
- Andrews, Philip C.,Busse, Madleen,Deacon, Glen B.,Ferrero, Richard L.,Junk, Peter C.,Huynh, Katie K.,Kumar, Ish,MacLellan, Jonathan G.
-
p. 9633 - 9641
(2011/01/05)
-
- Tetraphenylbismuth aroxides: Synthesis and structure
-
Tetraphenylbismuth aroxides Ph4BiOAr (Ar = C6H 3Cl2-2,6, C6H2(Br 2-2,6)(t-Bu)-4, C6H2(Br2-2,6) (NO2)-4 ? 1/2C6H6, C6H 3(NO2)2-2,4, C6H2(NO 2)3-2,4,6) were synthesized in the yield up to 90% by the reaction of pentaphenylbismuth with phenols and triphenylbismuth diaroxides and studied by X-ray diffraction. The Bi atoms of tetraphenylbismuth aroxides have a distorted trigonal-bipyramidal coordination with the axial O atom of the aroxide group. The axial angles CBiO vary from 171.7(2)° to 179.3(3)°. The distances Bi-O change in the interval 2.453(2)-2.925(7) A depending on the nature of substituents in the aromatic ring of the phenol residue. The increasing distance Bi-O in the series of compounds under study correlates with the tendency of the BiC4 fragment to form the tetrahedral configuration.
- Sharutin,Egorova,Sharutina,Pakusina,Pushilin
-
-
- Synthesis, structure, and reactivity of borate ester coordinated organobismuth compounds
-
A new class of hypervalent organobismuth compounds functionalized with coordinating pinacolborate esters of the nature ArBiCl2 (2), Ar 3Bi (3), ArPh2Bi (4), Ar3BiCl2 (5), and ArPh2BiCl2 (6), where Ar = 3-fluoro-2- pinacolatoboronphenyl, have been prepared and structurally characterized. The Bi ... O distance is between 2.58 and 3.47 A in the solid state for all compounds, and reasonable bonding interactions are presumed to exist in compounds 2-4 and 6, where Bi ... O 2BiCh (6) is exposed to CsF in the presence of furan, the [4 + 2] cycloaddition product of 3-fluorobenzyne + furan, 8, is isolated in 58% yield. Mechanistic evidence is offered to support the claim that 6 undergoes an unprecedented fluoride-promoted fragmentation to generate 3-fluorobenzyne, pinacol, BF3, and Ph2BiF.
- Carres, Christopher C.,Guccione, Samira
-
p. 747 - 752
(2009/01/30)
-
- Remarkable substituent effects on the oxidizing ability of tetraarylbismuthonium tetrafluoroborates in alcohol oxidation
-
Substituent effects on the oxidizing ability of tetraarylbismuthonium tetrafluoroborates in alcohol oxidation are reported. Intermolecular and intramolecular competition experiments on geraniol oxidation by the combined use of tetraarylbismuthonium tetrafluoroborates and N,N,N′,N′- tetramethylguanidine (TMG) have revealed that the oxidizing ability of the bismuthonium salt increases by the introduction of methyl groups at the ortho position and an electron-withdrawing group at the para position of the aryl ligands. The intermolecular and intramolecular H/D kinetic isotope effects observed for the competitive oxidation of p-bromobenzyl alcohols have shown that the present oxidation reaction consists of fast pre-equilibrium leading to alkoxytetraarylbismuth(V) intermediates (first step) and α-hydrogen abstraction by the aryl ligand attached to the bismuth (second step). The experimental results demonstrate that the electron-deficient aryl ligands enhance the electrophilicity at the bismuth center to put forward the first step and that the bulky ligands destabilize the alkoxybismuth(V) intermediates to accelerate the second step. The newly explored mesityl- and 2,6- xylyltriarylbismuthonium salts have proven to convert primary and secondary alcohols to the corresponding carbonyl compounds with high efficiency under mild conditions. A remarkable steric effect of these oxidants has also been exhibited in the chemoselective oxidation between primary and secondary benzylic alcohols.
- Matano, Yoshihiro,Suzuki, Takeshi,Iwata, Takaharu,Shinokura, Tomonori,Imahori, Hiroshi
-
p. 1621 - 1628
(2009/05/06)
-
- A new methodology for synthesis of aryl bismuth compounds: Arylation of bismuth(III) carboxylates by sodium tetraarylborate salts
-
Sodium tetraarylborate salts Na[BAr4] (Ar = C6H 3 (Ph), C6H4-MeA (tolyl), C6H 4-F-4) are found to be efficient arylating species for a range of bismuth(III) aromatic and aliphatic carboxylates including Bi(Hsal*) 3 (Hsal* = 2-HO-C6H4CO2 - (Hsal); 4-Me-2-HO-C6H3CO2 - (Hsal4Me); or 3-MeO-2-HO-C6H 3CO2- (Hsal3OMe)) and Bi(O 2CR)3 (R = Me, CMe3, and CF3) to produce triaryl bismuth compounds. The reactions may be carried out in ethanol, tetrahydrofuran, or acetone. The arylbismuth bis(salicylates) BiPh(Hsal) 2 and Bi(tolyl)(Hsal)2 exhibit similar reactivity in refluxing THF and may be used to produce mixed arylbismuthines BiPh x(tolyl)3-x. Formation of the known arylbismuth compounds was confirmed by IR spectroscopy, X-ray crystallography, NMR spectroscopy ( 1H, 11B, 13C, and 19F), and mass spectrometry. This is a facile synthesis of both symmetrical and unsymmetrical triarylbismuthines involving the aryl group transfer from the tetraarylborate ions to bismuth(III) under mild conditions.
- Stavila, Vitalie,Thurston, John H.,Prieto-Centurion, Dario,Whitmire, Kenton H.
-
p. 6864 - 6866
(2008/10/09)
-
- Palladium-catalyzed reaction of some triphenylbismuth(V) sulfonates and phenolates with methyl acrylate
-
Triphenylbismuth(V) derivatives Ph3BiX2 [X = OC 6H2(NO2)3-2,4,6, OC 6H2(NO2-4)Br2-2,6, OTs, OSO 2C6H4OH-4] react with methyl acrylate and PdCl2 (1:3:0.04 molar ratio) in acetonitrile at 20°C to form the cross-coupling products, methyl cinnamate (0.26-0.51 mol mol-1 starting bismuth compound) and methyl hydrocinnamate (0-0.17 mol mol -1); diphenyl, the homocoupling product (0-0.13 mol mol -1); and benzene (0.02-0.15 mol mol-1). The reaction of Ph3Bi(OSO2C6H4OH-4)2 is characterized by the selective formation of methyl cinnamate, but the reagent activity is low. Ph3Bi(OTs)2 exhibits the highest activity among the derivatives studied, but the reaction selectivity is low. The mechanisms of the palladium-catalyzed formation of homo-and cross-coupling products are proposed. Nauka/Interperiodica 2006.
- Gushchin,Malysheva,Kosov,Sharutin
-
p. 1249 - 1252
(2008/02/03)
-
- Palladium-catalyzed coupling of tetraphenylbismuth(V) derivatives with methyl acrylate
-
Tetraphenylbismuth(V) derivatives of the general formula Ph4BiX [X = OSO2C6H4Me-4, OC6H 2(NO2)3-2,4,6, OC6H 2(NO2-4)(Br2-2,6), OSO2C 6H3(OH)(COOH)] react with methyl acrylate in the presence of palladium dichloride (1:3:0.04 molar ratio) in acetonitrile at 20°C to form the cross-coupling products, methyl cinnamate (0.17-0.54 mol mol -1 starting bismuth compound) and methylhydrocinnamate (0.10-0.73 mol mol-1), diphenyl (0.06-0.80 mol mol-1), and benzene (0.02-0.36 mol mol-1). The highest C-phenylating activity is shown by Ph4BiOSO2C6H4Me-4. The mechanisms with the palladium-catalyzed cross-coupling reactions are suggested. Nauka/Interperiodica 2006.
- Gushchin,Malysheva,Kosov,Sharutin
-
p. 1253 - 1255
(2008/02/03)
-
- Synthetic and structural comparisons of bismuth(iii) carboxylates synthesised under solvent-free and reflux conditions
-
Two synthetic approaches to the formation of bismuth(iii) carboxylates have been explored and compared. Ph3Bi was reacted with a series of carboxylic acids (RCO2H) of varying pKa and functionality (R = PhCHCH, o-MeOC6H4, m-MeOC6H4, o-H2NC6H,, o-O2NC6H 4, p-O2NC6H4, 2-(C5H 4N)) under reflux conditions in toluene and solvent-free. The thermochemical profiles of the solvent-free reactions were also studied by DSC-TGA. All reactions produced the tri-substituted bismuth carboxylates in comparable yields and purity with the exceptions of picolinic acid and p-nitrobenzoic acid. 2-Picolinic acid exclusively formed the di-substituted complex, [PhBi(2-(C5H4N)CO2)2] 4, by both methods, while p-nitrobenzoic acid gave the tri-substituted complex through reflux and the di-substituted complex under solvent-free conditions. Two of the complexes were structurally authenticated by single crystal X-ray diffraction: [PhBi(2-(C5H4N)CO 2)2]4 is tetrameric formed through five membered chelate rings involving the pyridyl N and O(-C) rather than the less stable carboxylate (-CO2) chelates, while [Bi(o-MeOC 6H4CO2)3]∞, is a polymer in which dimeric units, constructed around two chelating and one unsymmetrical bridging carboxylate on each Bi centre, are then joined together through longer intermolecular Bi-O bridging bonds. The Royal Society of Chemistry 2006.
- Andrews, Philip C.,Deacon, Glen B.,Junk, Peter C.,Kumar, Ish,Silberstein, Morry
-
p. 4852 - 4858
(2007/10/03)
-
- Synthesis, structure and reactions of μ- oxobis(arenesulfonatotriarylbismuth)
-
Hydrolysis of triarylbismuth bis(arenesulfonates) in acetone gives bismuth derivatives of the general formula [Ar3Bi(OSO2Ar')] 2O (Ar = Ph, p-Tol; Ar' = Ph, C6H4Me-4, C 6H3Me2-2,4, C6H3Me 2-3,4). The structure of μ-oxobis[(3,4-dimethylbenzenesulfonato) triphenylbismuth] was established by means of X-ray diffraction. The molecule has a linear centrosymmetric structure with the bridging oxygen atom in the inversion center. The bismuth atom has a distorted trigonal bipyramidal coordination with the bridging oxygen atom and the arenesulfonate group in axial positions. The Bi-C and Bi-Oterm distances are 2.200(2), 2.204(3), and 2.442(2) A, and the Bi-Obr distances are 2.067(1) A. 2004 MAIK "Nauka/Interperiodica".
- Sharutin,Egorova,Sharutina,Ivanenko,Pavlushkina,Gerasimenko,Pushilin
-
p. 1359 - 1364
(2007/10/03)
-
- Diverse structures and remarkable oxidizing ability of triarylbismuthane oxides. Comparative study on the structure and reactivity of a series of triarylpnictogen oxides
-
A systematic series of triarylbismuthane oxides was prepared in order to disclose their structure and reactivity, which have been compared with those of lighter pnictogen counterparts. X-ray crystallographic analysis of tris(2-methoxyphenyl)bismuthane oxide and tris(2-methoxyphenyl)stibane oxide revealed that they exist as dimers with a flat bis(a-oxo) ring, implying that the polarized Bi+-O- and Sb+-O- bonds aggregate to attain electrostatic stabilization. In sharp contrast to their phosphorus, arsenic, and antimony counterparts, triarylbismuthane oxides are thermally unstable and possess a high oxidizing ability. In particular, the bismuthane oxides bearing ortho-substituted aryl ligands oxidized primary and secondary alcohols to aldehydes and ketones, respectively, with high efficiency under mild conditions.
- Matano, Yoshihiro,Nomura, Hazumi,Hisanaga, Teppei,Nakano, Haruyuki,Shiro, Motoo,Imahori, Hiroshi
-
p. 5471 - 5480
(2008/10/09)
-
- Phenylation of Organic Derivatives of Mercury, Silicon, Tin, and Bismuth with Pentaphenylantimony and Pentaphenylphosphorus
-
Pentaphenylantimony and -phosphorus react with arylmercury chlorides in toluene at room temperature to give diaryl derivatives of mercury in yields of up to 95%. The reactions of pentaphenylantimony and -phosphorus with silicon and tin halides involve ary
- Sharutin,Sharutina,Senchurin,Egorova,Ivanenko,Petrov
-
p. 202 - 203
(2007/10/03)
-
- Oxidizing ability of a series of (Tropon-2-ylimino)pnictoranes (Pnictogen = P, As, Sb, and Bi) toward some alcohols
-
In order to gain a better understanding of the oxidizing ability of a series of (tropon-2-ylimino)pnictoranes of the general structure Ph3M=NR (R = tropon-2-yl; M = P, As, Sb, and Bi), reactions were run with some alcohols such as benzopinacol (1,1,2,2-tetraphenyl-1,2-ethanediol), benzoin, cinnamyl alcohol, 1-phenylethanol, a mixture of cis- and trans-4-t-butylcyclohexanol, 2-phenylethanol, and 1-phenyl-1,3-propandiol. Iminophosphorane oxidized only benzopinacol to give benzophenone, while both arsorane and stiborane oxidized benzopinacol and benzoin to give benzophenone and benzil, respectively. On the other hand, iminobismuthorane has appreciable oxidizing ability, and reacted with the alcohols mentioned above, except the primary alcohol, to give the corresponding carbonyl compounds. Iminobismuthorane reacted with 1-phenyl-1,3-propandiol selectively to oxidize benzyl alcohol moiety, but not a primary alcohol moiety, to give 3-hydroxy-1-phenyl-1-propanone. Thus, the oxidizing ability of a series of (tropon-2-ylimino)pnictoranes is demonstrated to be in the order of iminophosphorane 3M+--NR canonical structure) and electrophilic character of pnictogen elements of a series of iminopnictoranes appear to increase their oxidizing ability when the pnictogen stands lower in the periodic table.
- Mitsumoto, Yuhki,Nitta, Makoto
-
p. 1029 - 1034
(2007/10/03)
-
- A novel dry route to ortho-functionalized triarylbismuthanes that are difficult to access by conventional wet routes
-
When an aryl iodide bearing an electron-withdrawing group at the ortho position was milled together with bismuth shots and calcite grains in the presence of Cu powder and CuI using a laboratory ball mill, the corresponding orthofunctionalized triarylbismuthane was obtained in moderate to good yield.
- Urano, Mika,Wada, Shinobu,Suzuki, Hitomi
-
p. 1202 - 1203
(2007/10/03)
-
- Tetraphenylbismuth 2,4-Dimethylbenzenesulfonate: Synthesis and Structure
-
Tetraphenylbismuth 2,4-dimethylbenzenesulfonate was synthesized by reacting pentaphenylbismuth or bromine with diphenylbismuth 2,4- dimethylbenzenesulfonate and its structure was established using X-ray diffraction analysis. The Bi atom has a distorted trigonal bipyramidal coordination. The Bi-C bond lengths are equal to 2.199(4)-2.227(4) A; the Bi-O distance and axial CBiO angle are equal to 2.665(3) A and 174.2(1)°, respectively.
- Sharutin,Egorova,Ivanenko,Sharutina,Pavlushkina,Gerasimenko
-
p. 317 - 321
(2008/10/08)
-
- Fluorotetraphenylbismuth: A new reagent for efficient regioselective α-phenylation of carbonyl compounds
-
Synthesis and X-ray crystallographic characterization of fluorotetraphenylbismuth (1) has been achieved for the first time, revealing that the bismuth center of 1 adopts a distorted trigonal bipyramidal geometry with three ipso carbons at the equatorial sites and one ipso carbon and fluorine atom at the apical sites. Contrary to the previous common understanding of this type of organobismuth(V) compound, 1 was found to be thermally stable, maintaining its amphiphilic property. Hence, 1 can be used as an off-the-shelf reagent in organic synthesis, and its utility has been clearly demonstrated in applications to the efficient α-phenylation of ketones and esters. For instance, simple mixing of 1 and 1-trimethylsiloxy-3,4-dihydronaphthalene in THF at -40 °C and stirring at room temperature for 10 min gave rise to 2-phenyl-1-tetralone almost quantitatively without formation of the polyphenylated products. In addition to the generality of this method, applicability of our approach to the selective α-alkenylation of carbonyl compounds was also demonstrated by the use of fluoro(2-phenylethenyl)tris(p-tolyl)bismuth (2) as a representative reagent. These results imply the vast potential of organobismuth(V) compounds of type 1 and 2 as useful precursors of a wide variety of pentavalent organobismuth compounds based on the utilization of the eminent fluorine-silicon interaction or the inherent basicity of the fluorine atom. Copyright
- Ooi, Takashi,Goto, Ryoji,Maruoka, Keiji
-
p. 10494 - 10495
(2007/10/03)
-
- Arylation of aryl- and diarylbismuth arenesulfonates with pentaarylantimony
-
Pentaarylantimony Ar3Sb (Ar = Ph, p-Tol) arylates diarylbismuth arylsulfonates Ar2BiOSO2Ar' (Ar' = C6H 4Me-4; C6H3Me2-2,4, C 6H3Me2-2,
- Sharutin,Egorova,Pavlushkina,Ivanenko
-
p. 1925 - 1926
(2007/10/03)
-
- A structural and mechanistic investigation of the mono-O-phenylation of diols with BiPh3(OAc)2
-
The mono-O-phenylation of enantiomerically pure pinanediol 2 using BiPh3(OAc)2 1 and the biphenyl-2,2′-ylenephenylbismuth analogue 9 has been investigated. It is postulated that reductive elimination at the trigonal bipyramidal bismuth (V) centre of 1 upon exposure to ambient light affects the transfer of an apical phenyl ligand to the least sterically encumbered hydroxyl group of the diol, affording the monophenyl ether in good yield. SbPh3(OAc)2 fails to undergo reductive elimination, affording the stable diolate 6 instead. The X-ray crystal structure of 6 provides a reasonable model for the intermediate of the bismuth mono-O-phenylation, and suggests further studies with bismuth complexes such as 9 possessing intramolecularly tethered ligands incapable of facilitating the mono-O-phenylation reaction. The discussions are supported by X-ray crystallographic correlations, and calculations indicate that (M)-(-)-6 adopts the lowest energy conformational diastereoisomer.
- Coles, Simon J,Costello, James F,Hursthouse, Michael B,Smith, Stephen
-
-
- Reactions of triarylbismuth bis(arenesulfonates)
-
Reactions of triphenylbismuth with sodium salts, acids, alkalies, and zinc are studied. In the first three cases Bi-O bond cleavage takes place, while zinc reduces the starting bismuth compounds to triphenylbismuth.
- Sharutin,Sharutina,Egorova,Ettenko
-
p. 1236 - 1237
(2007/10/03)
-
- Synthesis, structure, and reactivity of (tropon-2-ylimino)arsorane and in situ generation of its stiborane and bismuthorane analogues: Reactions with heterocumulenes and an activated acetylene giving heteroazulenes
-
(Tropon-2-ylimino)pnictoranes of the general structure RN=MPh3 (R = tropon-2-yl; M = As, Sb, and Bi) 4-6 have been prepared for the first time by the reaction of 2-aminotropone with Ph3MX2 (M = As, Sb, and Bi) in the presence of a base. The arsorane derivative (M = As) 4 is isolated as a stable crystalline compound, while the stiborane (M = Sb) and the bismuthorane (M = Bi) derivatives 5 and 6 are not isolated and are prepared in situ due to their moisture sensitivity. The X-ray crystal analysis revealed that compound 4 exhibits two different conformations in the solid state, and that the As-O bond distances (2.33 A) lie below the sum of the van der Waals radii (3.37 A), and thus, there is appreciable bonding interaction between the arsine and the oxygen atoms. With a view to constructing a series of cyclohepta-annulated heterocycles and in order to gain a better understanding of a series of iminopnictoranes, compounds 4-6 were allowed to react with heterocumulenes such as carbon disulfide, phenyl isothiocyanate, phenyl isocyanate, and diphenylcarbodiimide, in an aza-Wittig/electrocyclization or a formal [8 + 2] type cycloaddition eliminating triphenylpnictorane oxide to give 2H-cycloheptaoxazol-2-one, its thione, and imine derivatives. On the other hand, the reaction of compounds 4 and 5 with dimethyl acetylenedicarboxylate (DMAD) gives postulated dimethyl cyclohepta[b]pyrrole-2,3-dicarboxylate, which subsequently reacts with DMAD to result in the formation of tetramethyl 2H-cyclohepta[gh]pyrrolizine-1,2,4,5-tetracarboxylate, while the reaction of 6 gives only intractable tarry materials. The reactivity of the compounds 4-6, which contain a formal N=M (M = As, Sb, and Bi) double bond, has been clarified to be in the order of 6 (M = Bi) > 5 (M = Sb) > 4 (M = As) > [the corresponding iminophosphorane derivative 3 (M = P)].
- Nitta,Mitsumoto,Yamamoto
-
p. 1901 - 1907
(2007/10/03)
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- Arylation of organotin halides with pentaarylantimony and pentaphenylbismuth
-
Pentaarylantimony and pentaphenylbismuth arylate oranotin halides R3SnX and R2SnX2 (R = Alk, Ar; X = Cl, Br) in toluene at room temperature to aryltin derivatives R3SnAr and R2SnArX (initial reagent molar ratio 1:1) or R2SnAr2 (2:1) in 78-95% yield.
- Sharutin,Sharutina,Senchurin,Kovaleva,Shcherbakov,Gladyshev
-
-
- Synthesis, structure, and reactions of triaryl(methyl)bismuthonium salts
-
Treatment of triarylbismuth difluorides 2 (Ar3BiF2; a, Ar = Ph; b, Ar = 4-MeC6H4; c, Ar = 4-MeOC6H4; d, Ar = 2-MeOC6H4) with methylboronic acid (3) in the presence of BF3·OEt2 in CH2Cl2 afforded the corresponding triaryl(methyl)bismuthonium tetrafluoroborates 4a-d ([Ar3MeBi+][BF4-]) in 42-91% yield. X-ray crystallographic analysis of compound 4d revealed that the bismuth center possesses a distorted tetrahedral geometry with C-Bi-C bond angles of 106.1(3)-113.6(3)° and Bi-C bond lengths of 2.182(7)-2.195(8) angstrom. Compound 4a transferred the methyl group to Ph3E (E = P, As, Sb), tris(4-methylphenyl)bismuthine, ROH (R = Me, Et, i-Pr, PhCH2), water, sodium benzenesulfinate, sodium benzoate, N,N-dimethylformamide (DMF), and thioacetamide to give the corresponding methylated products with a good recovery of triphenylbismuthine. The pseudo-first-order rate constant (kobsd = 2.9 × 10-4 s-1) observed for the reaction between 4a and benzyl alcohol (5d) was about twice as large as that (kobsd = 1.3 × 10-4 s-1) between MeOTf and 5d (in CDCl3 at 23°C; [4a] or [MeOTf] = 0.062 M; [5d] = 0.97 M). The observed reactivity of 4a clearly demonstrates the high nucleofugality of the triphenylbismuthonio group.
- Matano, Yoshihiro
-
p. 2258 - 2263
(2008/10/08)
-
- Reaction of pentaphenylantimony with triphenylbismuth diacylates
-
Reactions of pentaphenylantimony with triphenylbismuth diacylates yield the corresponding tetraphenylantimony acylates. Triphenylbismuth bis(trichloroacetate) was prepared by oxidation of triphenylbismuth with hydrogen peroxide in the presence of trichloroacetic acid. The structure of triphenylbismuth dibenzoate was determined by single crystal X-ray diffraction. The coordination polyhedron of the central atom is intermediate between trigonal bipyramid and pentagonal bipyramid; the benzoate groups occupy the equatorial position.
- Sharutin,Sharutina,Egorova,Senchurin,Ivashchik,Bel'skii
-
p. 873 - 875
(2007/10/03)
-
- Palladium(II)-catalyzed aryl coupling of triarylbismuthines under air
-
Triarylbismuthines readily reacted with a catalytic amount of palladium(II) acetate in methanol under air to give the corresponding biaryls in high yields. The presence of oxygen was indispensable for this catalytic coupling, biaryl formation being quite slow under nitrogen. Oxygen absorption was observed during the reaction and a Pd-oxygen complex prepared separately worked effectively as a reagent for this coupling even under inert gas.
- Ohe, Toshiyuki,Tanaka, Takumi,Kuroda, Masashi,Cho, Chan Sik,Ohe, Kouichi,Uemura, Sakae
-
p. 1851 - 1855
(2007/10/03)
-
- Synthesis and structure of tetra- and triphenylbismuth arenesulfonates
-
Tetraphenylbismuth arenesulfonates were synthesized by the reaction of pentaphenylantimony or -bismuth with triphenylbismuth bis(arenesulfonates). Triphenylbismuth bis(arenesulfonates) were synthesized by the reaction of triphenylbismuth with arenesulfonic acids in the presence of hydrogen peroxide. The crystal structures of the tetraphenylbismuth 2,5-dimethylbenzenesulfonate crystal hydrate (1), tetraphenylbismuth 3-carboxy-4-hydroxybenzenesulfonate (2), and triphenylbismuth bis(2,5-dimethylbenzenesulfonate) (3) were determined by X-ray diffraction analysis. The Bi atom in 1 has a tetrahedral coordination (bond angles vary from 106.6(6) to 111.9(10)°). The Bi coordination observed in 2 is intermediate between tetrahedral and trigonal-bipyramidal, and that in structure 3 is trigonal-bipyramidal, with the oxygen atoms in the axial positions. The Bi - O bond lengths are 2.19(2) and 2.27(2) A. In the crystal of 2, the anions form an infinite hydrogen-bonded chain.
- Sharutin,Sharutina,Egorova,Kharsika,Lodochnikova,Gubaidullin,Litvinov
-
p. 2325 - 2329
(2007/10/03)
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- Di(tert-butylperoxy)triphenylbismuth and the triphenylbismuth - tert-butyl hydroperoxide system as efficient oxidants of alcohols
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Di(tert-butylperoxy)triphenylbismuth and the triphenylbismuth - tert-butyl hydroperoxide system react with aliphatic alcohols and cyclohexanol to give carbonyl compounds in high yields. The oxidation occurs as the radical dehydrogenation of alcohols; Bi derivatives serve as the sources of free radicals.
- Zinov'eva,Dolganova,Dodonov,Prezhbog
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p. 659 - 662
(2007/10/03)
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- Two-step synthesis of triarylmetals (As, Sb, Bi) starting from the metal oxides and 2,6-dimethoxybenzenethiol
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Reported here is a new synthetic method of triarylmetals MAr3 (M = As, Sb, Bi). It is composed of two-step reactions starting from the metal oxides: (1) A reaction of the metal oxide with 2,6-dimethoxybenzenethiol ΦSH [Φ = 2,6-(MeO)2C6H3] in the presence of acid to give the thiolatometals M(SΦ)3, and (2) A reaction of M(SΦ)3 with organolithium reagent LiAr to give MAr3 (Ar = Ph, 4-MeC6H4, 4-Me2NC6H4, Φ). Since ΦSH is odorless and crystalline, most of it can be recovered after the reactions without difficulty for repeated usages. The intermediates M(SΦ)3 are also crystalline and inert against hydrolysis.
- Wada, Masanori,Natsume, Satoko,Suzuki, Shinobu,Uo, Akira,Nakamura, Michiaki,Hayase, Shuichi,Erabi, Tatsuo
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p. 223 - 227
(2007/10/03)
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