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 Bis(tetraphenylantimony) Tetrafluorophthalate

Oxidation of pentaphenylantimony with atmospheric oxygen in toluene on heating gives -oxo-bis(tetraphenylantimony) (yield 63%). Its reaction with tetrafluorophthalic anhydride gives bis(tetraphenylantimony) tetrafluorophthalate (yield 94%). According to single-crystal X-ray diffraction data, the antimony atoms in the molecule of bis(tetraphenylantimony) tetrafluorophthalate have a distorted trigonal bipyramidal coordination with the following geometries: Sb-O bond lengths 2.357(3) and 2.283(3) Å, Sb-C bond lengths 2.108(4)-2.141(4) and 2.100(5)-2.158(4) Å, and CSbO angles 177.42(14)° and 176.18(14)°.     

Bismuth(III) Halide Complexes: New Structural Types and New Application Areas

Recent advances in studies of bismuth(III) halide complexes (HBs) are reviewed concisely. New structural types of HBs and some of their physical properties that show the greatest promise for application and attract the greatest attention of researchers are discussed.     

Activation of C-F bonds in ionic liquids catalyzed by nickel complex compounds

A nickel complex-catalyzed hydrodefluorination of acet(pentafluoroanilide) with zinc in ionic liquids resulted in the corresponding 2,3,4,5-tetrafluoro, 3,4,5-trifluoro, and 3,4-difluoro derivatives. The influence of the ionic liquid nature and the reaction conditions on its selectivity were studied, a possibility of the multiple reuse of the ionic liquids as the reaction media was demonstrated.     

CRYSTAL STRUCTURES OF BINUCLEAR CHLOROBISMUTHATE COMPLEXES WITH 3-METHYLPYRIDINIUM AND 4-IODOPYRIDINIUM CATIONS

Journal of Structural Chemistry - Reactions of Bi2O3 solutions in 2M HCl with 3-methylpyridine and 4-iodopyridine result in the formation of binuclear Cat4[Bi2Cl10] complexes...     

Perylene derivatives formation in reaction of 3-bromobenzanthrone and 4-bromonaphthalic acid derivatives with a reduction system NiCl2-2,2′bipyridyl (or 1,10-phenathroline)-Zn

The reaction of 3-bromobenzanthrone and 4-bromonaphthalic acid derivatives with a reduction system NiCl₂-2,2′bipyridyl (or l,10-phenathroline)-Zn gives rise to compounds containing perylene fragment. Under similar conditions was established a possibility to transform substituted l.l′-binaphthyls into the corresponding perylene derivatives. The study was carried out under financial support of the State Research Center “NIOPIK” (grant no.528/93-1679).     

Crystal structures of binuclear Bi(III) chloride and bromide complexes with some cations — Alkylated pyridine derivatives

By a reaction of [BiX₆]^3– with salts of various N-alkylated pyridine derivatives in 2M HX (X = Cl, Br), (N-BzPy)₄[Bi₂X₁₀] complexes (X = Cl (1), Br (2), (4-MePyH)₄[Bi₂Cl₁₀] (3)) are obtained and structurally characterized.     

Supramolecular Systems Based on Ca2+, [Mo3O2S2Cl6(H2O)3]2s-, [Mo3S4Cl6.75Br0.25(H2O)2]3s- and Cucurbit[6]uril

Adducts of cucurbit[6]uril with Ca²⁺ and trinuclear cluster chloroaquacomplexes (H₉O₄)₂(H₇O₃)₂[(Ca(H₂O)₅)2(C₃₆H₃₆N₂₄O₁₂)]Cl₈·0.67H₂O (1) and [(Ca(H₂O)₅)₂(C₃₆H₃₆N₂₄O₁₂)]× [Mo₃O₂S₂Cl₆(H₂O)₃]₂·13H₂O (2) are obtained and structurally characterized. The structures of both compounds contain polymeric [Ca(H₂O) _n ]₂² CB[6]∞ cations that form infinite columns; the space between them is filled with Cl^s- (1) and [Mo₃O₂S₂Cl₆(H₂O)₃]^2s- (2). A new (H₇O₃)₂(H₅O₂)× [Mo₃S₄Cl_6.25Br_0.25(H₂O)₂](C₃₆H₃₆N₂₄O₁₂)·CH₂Cl₂·6H₂O complex (3) is also obtained and structurally characterized.     

Synthesis and crystal structure of [W3S4(Acac)3(PPh3)3]PF6 · 0.5CHCl3 and [W3S4(Hfac)3(PPh3)2Br] · 2CHCl3

New cluster complexes [W₃S₄(Acac)₃(PPh₃)₃]PF₆ · 0.5CHCl₃ (Acac = CH₃C(O)CHC(O)CH₃) (I) and [W₃S₄(Hfac)₃(PPh₃)₂Br] · 2CHCl₃ (Hfac = CF₃C(O)CHC(O)CF₃) (II) were synthesized. Their molecular and crystal structures were determined by X-ray diffraction. The cis-cis type of coordination of acetylacetonate and hexafluoroacetylacetonate ligands in I and II, respectively, was established, and the PPh₃ ligands were found in the trans-positions with respect to the “capping” sulfide ligand (μ³-S).