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.     

Synthesis and Structure of Tetraphenylantimony Phenoxyacetate and Ethylmalonate Ph4SbOC(O)R (R = CH2OPh and CH2C(O)OC2H5)

Tetraphenylantimony phenoxyacetate (I) was synthesized by reacting pentaphenylantimony with phenoxyacetic acid (at a molar ratio of 1 : 1) in toluene. Tetraphenylantimony ethylmalonate (II) was synthesized from triphenylantimony and malonic ether in the presence of hydrogen peroxide (1 : 1 : 1) in diethyl ether. According to X-ray diffraction data, Sb atoms in compounds I and II have a distorted trigonal bipyramidal coordination to the axial oxygen atoms. The axial OSbC_ax angles and Sb-C_ax distances are, respectively, 176.31(6)° and 2.177(2) Å for I and 179.40(4)° and 2.162(1) Å for II. The Sb-C_eq distances lie in the intervals of 2.108(2)-2.127(2) Å for I and 2.117(1)-2.128(1) Å for II. In compounds I and II, the Sb-O bond lengths are equal to 2.235(1) Å and 2.250(1) Å, respectively, and the intramolecular contacts Sb··· are equal to 3.402(2) Å and 3.282(1) Å, respectively.     

Synthesis and structure of bismuth-containing complexes [(Ph4BiO)2{2,5-(CH3)2C6H3S(O)}] 2 + [Ph2Bi2I6]2−,[(Ph4Bi]+[PhBi(C5H5N)I3]−, [Ph4Sb] 4 + [Bi4I16]4−⋅2(CH3)2 C=O, and [Ph4Sb] 3 + [Bi5I18]3−

The reactions of tetraphenylbismuthonium and -stibonium salts Ph₄EX (E = Bi, Sb; X = I, OSO₂ (C₆H₃(CH₃)₂-2,5), OSO₂C₆H₃(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph₄Bi]⁺[PhBi(C₅H₅N)I₃]^-, [(Ph₄BiO)₂S(O){2,5-(CH₃)₂C₆H₃S(O)} [Ph₂Bi₂I₆]^2–, [Ph₄Sb [Bi₄I₁₆]^4-·2(CH₃)²C=O, and [Ph₄Sb] ₃₊ ⁺ [Bi₅I₁₈]^3-, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.     

4-Methoxy-3-methylgoniothalamin from marine-derived fungi of the genus Penicillium

The new styrylpyrone derivative, viz. 4-methoxy-3-methylgoniothalamin (1), and the known compound sulochrin were isolated from the marine-derived fungi Penicillium glabrum and P. implicatum. The structure of compound 1 was determined by X-ray diffraction, 2D NMR spectroscopy, and high-resolution mass spectrometry. It was shown for the first time that sulochrin increases expression of the protein Hsp70.     

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.     

Disordering of the [NbOF5]2− complex anions in bis(glycinium) pentafluoridooxidoniobate(V) and bis(β‐alaninium) pentafluoridooxidoniobate(V) dihydrate

The title compounds, (C₂H₆NO₂)₂[NbOF₅], (I), and (C₃H₈NO₂)₂[NbOF₅]·2H₂O, (II), are built from isolated distorted octahedral [NbOF₅]²⁻ complex anions, amino acid cations and water molecules [for (II)]. In the pentafluoridooxidoniobate(V) anions, the Nb and O atoms, and the F atoms in trans positions with respect to the O atoms, are disordered about an inversion centre for both structures. The Nb atoms are shifted from the inversion centres by distances of 0.1455 (1) and 0.1263 (2) Å for (I) and (II), respectively. The Nb=O and Nb—F(trans) bond lengths are 1.7952 (3) and 2.0862 (3) Å, respectively, for (I), and 1.8037 (7) and 2.0556 (7) Å for (II). In the crystal structures, cations and water molecules [for (II)] are linked to the [NbOF₅]²⁻ anions via hydrogen bonds. This study demonstrates the possibility of true geometry determination of disordered [NbOF₅]²⁻ complex anions in centrosymmetric structures.     

Synthesis and structures of mercury and cadmium complexes: [Ph4Sb] 2 + [Hg2I6]2−·Ph2Hg, [Ph4Sb] 2 + [E2I6]2− (E = Hg, Cd), and [Ph4Sb] 2 + [Hg4I10]2−

The reaction of pentaphenylantimony with mercury iodide affords the ionic complex [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2?·Ph₂Hg (I). The [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2? (II) and [Ph₄Sb] ₂ ⁺ [Cd₂I₆]^2? (III) complexes are synthesized from tetraphenylantimony iodide and mercury and cadmium iodides. The [Ph₄Sb] ₂ ⁺ [Hg₄I₁₀]^2? complex (IV) is prepared from tetraphenylantimony 2,4-dimethylbenzenesulfonate and mercury iodide. According to the X-ray diffraction data, the Sb atom in the [Ph₄Sb]⁺ cations of complex I has virtually ideal tetrahedral coordination (the CSbC angles are 108.09°–109.64°). In the central square fragment Hg₂I₂ of the [Hg₂I₆]^2? anion, the Hg-I_br bond lengths are 2.825 and 3.075 Å, and the terminal iodine atoms are more strongly bonded to the mercury atoms (Hg-I_term 2.691 and 2.700 Å). The [Cd₂I₆]^2? anion in complex III has a similar structure (the Cd-I_bridg and Cd-I_term distances are 2.865, 2.872 and 2.723, 2.748 Å, respectively). The anions in complex IV are joined by I…Hg (3.651 Å) and I…I (4.058 Å) interactions into an infinite dimeric network.     

Synthesis and Structure of Bismuth Tris(3-Methylbenzoate) [Bi(O2CC6H4CH3-3)3]∞ and Phenylbismuth Bis(3,4,5-Trifluorobenzoate) [PhBi(μ-O2CC6H2F3-3,4,5)(O2CC6H2F3-3,4,5)]2

Bismuth tris(3-methylbenzoate) [Bi(O₂CC₆H₄CH₃-3)₃] (I) and phenylbismuth bis(3,4,5-trifluorobenzoate) [PhBi(-O₂CC₆H₂F₃-3,4,5)(O₂CC₆H₂F₃-3,4,5)]₂ (II) were synthesized by reacting triphenylbismuth with 3-methylbenzoic and 3,4,5-trifluorobenzoic acids. Coordination numbers of bismuth atoms in I and II are 9 and 6, respectively; carboxylate ligands function as bi- and tridentate ligands. The Bi-O distances in compound I vary in the range of 2.218(3)-3.202(4) Å. The Bi-O and Bi-C bond lengths in II are 2.301(2)-2.674(2) and 2.223(3) Å, respectively.     

Synthesis and study on oxidative coupling products of 3-alkyl-2-hydroxynaphthazarins

The resulting products of oxidative coupling of substituted 3-alkyl-2-hydroxynaphthazarins in the presence of lead dioxide are the compounds with 7,14-dibenzo[a,i]oxanthrene skeleton.