Bismuth-ferrocene carboxylates: synthesis and structure

The reaction of ferrocenedicarboxylic acid with triphenylbismuth in a 1?:?1 ratio under solvothermal conditions afforded the 1D coordination polymer [Bi(2)(μ(2)-η(2)-OOCFcCOO-μ(2)-η(2))(η(2)-OOCFcCOO-η(2))(μ(2)-η(2)-OOCFcCOO-η(2))](n) (1). In this polymer two types of bismuth centers (hepta- and octacoordinate) are present and are interconnected by the bridging coordination of ferrocene dicarboxylate ligands. The reaction of ferrocenecarboxylic acid with triphenylbismuth in a 1?:?3 ratio, in toluene, under refluxing conditions, afforded the 1D coordination polymer [Bi(μ(2)-η(2)-FcCOO)(η(2)-FcCOO)(2)](n) (2). In the solid state, 2 exists as a helical polymer, where the inner bismuth chain is enclosed by an external sheath of ferrocene carboxylate ligands. In solution, however, 2 decomposes into the monomeric repeat unit [Bi(FcCOO)(3)] which is indicated by ESI-MS as well as cyclic voltammetric studies. Thus, a single, quasi-reversible redox event is seen for 2 in solution. The reaction of triphenylbismuth with ferrocenecarboxylic acid in a 1?:?1 stoichiometry afforded the molecular dimer [Bi(2)(μ(2)-η(2)-FcCOO)(2)(η(2)-FcCOO)(4)(H(2)O)(4)]·(2FcCOOH) (3). Compounds 1-3 reveal rich supramolecular architectures in the solid state as a result of the presence of C-HO, C-Hπ and ππ interactions.     

Synthesis and Structure of Triphenylbismuth Dinitrite and Dinitrate

Triphenylbismuth dinitrate (I) and triphenylbismuth dinitrite (II) were synthesized through the reaction of triphenylbismuth dichloride with silver nitrate in an acetone–alcohol (1 : 1) solution or with sodium nitrite in acetone–water (1 : 1) solution. According to X-ray diffraction data, bismuth atoms in Iand II have a distorted trigonal bipyramidal configuration. The intramolecular Bi···N(1,2) contacts in II (2.997(3), 2.982(4) Å) are shorter than similar contacts in I(3.038(3), 3.031(3) Å); the Bi···O(2,4) distances in II and Bi···O(2,5) distances in I are equal to 2.879(2), 2.913(3) and 2.893(3), 2.896(3) Å, respectively.     

Tris(1-adamantanecarboxylato)bismuth(III): Synthesis and structure

Tris(1-adamantanecarboxylato)bismuth(III) was synthesized by reacting triphenylbismuth with 1-adamantanecarboxylic acid in toluene. The bismuth atom in tetramer {Bi[OC(O)C₁₀H₁₅]₃}₄ is coordinated by 10 oxygen atoms of bidentate-chelating and two types of chelate-bridging adamantanecarboxylate ligands (Bi-O, 2.191–2.955 and 3.634 Å).     

New Synthesis of Triphenylbismuth Diaroxides

The reaction of triphenylbismuth, hydrogen peroxide, and phenol (molar ratio 1 : 1 : 2) in ether was used to synthesize triphenylbismuth diaroxides Ph₃Bi(OAr)₂ [Ar = C₆H₃(NO₂)₂-2,4, C₆H₂(NO₂)₃-2,4,6, C₆H₃Cl₂-2,6, C₆H₂Cl₃-2,4,6, C₆H₃Br₂-2,4, C₆H₂Br₃-2,4,6, C₆H₂Br₂-2,4,Me-6, C₆H₂Br₂-2,6, NO₂-4]. At an equimolar reagent ratio, bridged bismuth compounds (Ph₃BiOAr)₂O are formed. The crystal structure of bis-(2,4-dinitrophenoxy)triphenylbismuth Ph₃Bi[OC₆H₃(NO₂)₂-2,4]₂ was studied by X-ray diffraction to show that the bismuth atom has a distorted trigonal bipyramidal coordination and the 2,4-dinitrophenoxyl ligands are axial. The CBiC and OBiO angles are 109.6(5)°, 122.3(5)°, 128.1(5)°, and 175.6(3)°. The Bi-O^1,6 and Bi-C bond lengths are 2.256(10), 2.242(9) and 2.18(1), 2.18(1), 2.19(1) Å, respectively.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 927–929.Original Russian Text Copyright © 2005 by Sharutin, Egorova, Tsiplukhina, Molokov, Fukin.     

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.     

The chemistry of orqanobismuth reagents: Part XIII ligand coupling induced by Pd(O)

Palladium zero converts triphenylbismuth quantitatively to diphenyl and metallic bismuth. Many other derivatives of Bi (III) and Bi(V) are similarly transformed to diaryls in excellent yield. Similar reactions with triphenylantimony and with perphenyl lead derivatives suggest that a number of non-transition metal elements should show similar behaviour.Acid chlorides also react under mild conditions with triphenylbismuth under catalysis by palladium (O) to furnish phenylketones in excellent yield (with respect to the triphenylbismuth). All three phenyls are transferred when a suitable excess of the acid chloride is used. Diaryl formation is a minor side reaction.     

Phenylbismuth Bis(2,5-dimethylbenzenesulfonate): Structure and properties

Phenylbismuth bis(2,5-dimethylbenzenesulfonate) (I), a coordination polymer in which a bismuth atom has a distorted square pyramidal coordination to an axial carbon atom (Bi-C, 2.247(5) Å) and basal oxygen atoms (Bi-O, 2.390(9)–2.403(10) Å), has been synthesized by the reaction between triphenylbismuth and 2,5-dimethylbenzenesulfonic acid (1: 2 mol/mol) in toluene and structurally characterized. Pentaphenylbismuth and pentaphenylantimony phenylate compound I to triphenylbismuth.     

Synthesis and structure of 2,4,6-tribromophenoxytetraphenylbismuth

Four new complexes of pentavalent bismuth are synthesized: Ph₃Bi[OC₆H₂(Br₃-2,4,6)]₂, Ph₃Bi[OC₆H₂(Cl₃-2,4,6)]₂, Ph₄BiOC₆H₂(Br₃-2,4,6), and Ph₄BiOC₆H₂(Cl₃-2,4,6). Tetraphenylbismuth aroxides are produced by the disproportionation reaction of ligands from pentaphenylbismuth and triphenylbismuth diaroxides in toluene or from pentaphenylbismuth and phenol. Triphenylbismuth diaroxides are synthesized from phenol, triphenylbismuth, and hydrogen peroxide taken at a molar ratio of 2 : 1 : 1, respectively, in diethyl ether. According to the X-ray diffraction data, the bismuth atom surrounding in 2,4,6-tribromophenoxytetraphenylbismuth has the configuration of a trigonal bipyramid with the aroxyl ligand in the axial position. The Bi-C and Bi-O bond lengths are 2,184, 2.190, 2.234, and 2.514 Å, respectively, and the equatorial CSbC angles are equal to 111.4°, 121.3°, and 121.3°.Translated from Koordinatsionnaya Khimiya, Vol. 30, No. 12, 2004, pp. 935–938.Original Russian Text Copyright © 2004 by Sharutin, Egorova, Tsiplukhina, Gerasimenko, Pushilin.     

An unusual pathway of the oxidation of diethyl ether by bismuth(v) derivatives

Di(tert-butylperoxy)triphenylbismuth and the triphenylbismuth-tert-butyl hydroperoxide system transform diethyl ether into ethoxyacetic aldehyde. The latter undergoes further conversions under these reaction conditions to give the corresponding hydroxyperoxide, ethoxyacetic acid, and bismuth(III) acylates.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 783–784, April, 1995.This work was financially supported by the Competition Center for Fundamental Natural Studies at Saint-Petersburg University (Grant No. 94-9.4-219).     

The first bismuth phosphonate cluster. X-ray single crystal structure of [(ButPO3)10(ButPO3H)2Bi14O(10).3C6H(6).4H2O

The reaction of triphenylbismuth and tert-butylphosphonic acid gives the bismuth phosphonate phase (ButPO3H)3Bi and the first bismuth phosphonate cluster [(ButPO3)10(ButPO3H)2Bi14O(10).3C6H(6).4H2O].     

Synthesis and structure of triphenylbismuth bis(2-phenylaminobenzoate)

Interaction of triphenylbismuth with phenylanthranilic acid in the presence of hydrogen peroxide yields triphenylbismuth bis(2-phenylaminobenzoate), in which bismuth atoms have a distorted trigonal bipyramidal coordination with phenyl ligands in equatorial positions. The bond lengths (Å) are as follows: Bi-C, 2.193(5), 2.200(4), and 2.200(4); Bi-O, 2.252(4) and 2.300(4). Intramolecular hydrogen bonds N-H?O(=C) (H?O, 1.91, 1.97 Å; N?O, 2.634(9), 2.667(9) Å) and donor-acceptor interactions Bi?O(=C) (2.790(5) and 2.838(5) Å) exist in the molecule.     

Triphenylbismuth Bis(2,4,6-Tribromophenoxide): Synthesis and Structure

A reaction of triphenylbismuth with 2,4,6-tribromophenol and hydrogen peroxide (molar ratio 1 : 2 : 1) in ether affords triphenylbismuth bis(2,4,6-tribromophenoxide). The complex obtained was structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Bi atom is a trigonal bipyramid with axial aroxy groups. The Bi–C and Bi–O bond lengths are 2.202(4), 2.203(4), 2.212(4) and 2.241(3), 2.245(3) Å, respectively. The intramolecular Bi···Br(1,4) contacts are 3.629(1) and 4.077(1) Å, respectively.     

The chemistry of pentavalent organobismuth reagents : Part IX. Cleavage reactions of α-glycols

A catalytic bismuth system (Ph₃Bi-NBS-K₂CO₃-CH₃CN with 1% water) for the cleavage of α-glycols is shown to have a different mechanism from the cyclic process observed with the stoichiometric Bi^V reagents previously studied. The catalytic system cleaves cis- and trans-decalin-9,10-diols at nearly the same rate, whereas the stoichiometric system does not cleave the trans-9,10-diol. Evidence for the insertion of triphenylbismuth into a hypobromite bond followed by fragmentation of the thus formed Bi^V intermediate has been secured.     

Synthesis and structure of triphenylbismuth bis(phenylcarboranylcarboxylate)

Triphenylbismuth bis(phenylcarboranylcarboxylate) was synthesized by the reaction of triphenylbismuth with phenylcarboranylcarboxylic acid in the presence of hydrogen peroxide. The bismuth atom has a distorted trigonal-bipyramidal coordination with phenyl ligands in equatorial positions. Bond lengths: Bi-C 2.195(3), 2.196(3), 2.204(3) Å, Bi-O 2.266(2), 2.276 Å. In the molecule there are the donor-acceptor interaction of Bi...O(=C) 2.980(2) and 3.130(3) Å. The value of the equatorial angle CBiC from the side of the Bi...O(=C) contact is 141.4(1)°, the angle OBiO is 168.2(1).     

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)°.     

Photochemical synthesis of bismuth selenide nanocrystals in an aqueous micellar solution

The photolytic decomposition of triphenylbismuth and di-tert-butyl diselenide under aqueous micellar conditions yields 5-nm bismuth selenide nanocrystals of the BiSe stoichiometry. This is the first example of the bismuth-rich BiSe phase being prepared in a well-dispersed colloidal nanocrystal form.     

Synthesis and Structure of Triphenylbismuth Bis(Fluorobenzoates)

The reaction between triphenylbismuth, hydrogen peroxide, and 3,4,5-trifluorobenzoic or pentafluorobenzoic acid (molar ratio 1 : 1 : 2, respectively) in ether gave triphenylbismuth bis(3,4,5-trifluorobenzoate) (I) and triphenylbismuth bis(pentafluorobenzoate) (II) in 74 and 89% yields, respectively. The structures of compounds I and II were established by X-ray diffraction. The Bi atoms have a distorted trigonal-bipyramidal coordination with acylate groups in the axial positions. The OBiO angles are 170.2(2)° and 171.5(2)° in I and II, respectively. The Bi–C(Ph)_eq bond lengths vary in the range of 2.187(6)–2.204(5) Å, the Bi–O(acyl) lengths are 2.256(5) Å in I, and 2.281(5) and 2.318(5) Å in II. In the crystals I and II, the Bi and carbonyl O atoms are involved in intramolecular interactions (Bi···O(=C) 2.926(5)–3.176(5) Å), which increase the equatorial CBiC angles on the side of these contacts to 136.2(3)° and 138.6(2)° in I and II, respectively.     

Synthesis and structure of tetra- and triphenylbismuth arenesulfonates

Tetraphenylbismuth arenesulfonates were synthesized by the reaction of pentaphenylantimony of-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 in1 has a tetrahedral coordination (bond angles vary from 106.6(6) to 111.9(10)^o). The Bi coordination observed in2 is intermediate between tetrahedral and trigonal-bipyramidal, and that in structure3 is trigonal-bipyramidal, with the oxygen atoms in the axial positions. The Bi−O bond lengths are 2.19(2) and 2.27(2) Å. In the crystal of2, the anions form an infinite hydrogen-bonded chain. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2350–2354, December, 1999.     

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, C₆H₃Me₂-2,4, C₆H₃Me₂-3,4). The structure of -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-O_term distances are 2.200(2), 2.204(3), and 2.442(2) Å, and the Bi-O_br distances are 2.067(1) Å.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1466–1471.Original Russian Text Copyright © 2004 by Sharutin, Egorova, Sharutina, Ivanenko, Pavlushkina, Gerasimenko, Pushilin.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis and structure of triphenylbismuth bis(pentachlorobenzoate)

Triphenylbismuth bis(pentachlorobenzoate) has been synthesized by the reaction between triphenylbismuth and pentachlorobenzoic acid in the presence of hydrogen peroxide in ether. According to X-ray diffraction data, the bismuth atoms in two crystallographically independent molecules (A and B) have a distorted trigonal bipyramidal coordination. The OBiO and CBiC angles between axial and equatorial substituents are 171.7(3)°, 173.6(3)°, and 105.3(4)°–146.9(4)°. The Bi-O and Bi-C bond lengths are 2.291(8)–2.315(8) and 2.197(11)–2.204(10) Å, respectively. The Bi…O(=C) distances are 2.843(10)–2.857(11) Å.