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.     

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 Crystal Structure of Tetraphenylbismuth Benzenesulfonate Hydrate and Tetraphenylbismuth 3,4-Dimethylbenzenesulfonate

The reaction of pentaphenylbismuth with SO₃ or with triphenylbismuth bis(benzenesulfonate) in benzene gave tetraphenylbismuth benzenesulfonate monohydrate (I). Tetraphenylbismuth 3,4-dimethylbenzenesulfonate (II) was prepared from pentaphenylbismuth and triphenylbismuth bis(3,4-dimethylbenzenesulfonate) in benzene. The structures of compounds I and II were established by X-ray diffraction. The Bi atoms have a distorted trigonal-bipyramidal coordination where the arenesulfonate group occupies an axial position. The Bi–C(average) and Bi–O distances in molecules I and II are 2.204(2), 2.695(2) Å and 2.205(2), 2.728(2) Å, respectively.     

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) Å the Bi–O distance and axial CBiO angle are equal to 2.665(3) Å and 174.2(1)°, respectively.     

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.     

Reaction of Tetraphenylantimony Bromide with o-Tolylbismuth Bis(2,5-dimethylbenzenesulfonate). The Formation of Tetranuclear Anion [Bi4Br16]4–

The [Ph₄Sb]₄[Bi₄Br₁₆] complex was synthesized via reaction of tetraphenylantimony bromide with o-tolylbismuth bis(2,5-dimethylbenzenesulfonate) and studied using X-ray diffraction analysis. This compound has ionic structure and consists of tetraphenylstibonium cations and a four-charge tetranuclear anion [Bi₄Br₁₆]^4– formed by two pairs of edge-sharing iBr₆ octahedra. The Sb–C bond lengths are equal to 2.05(1)–2.10(1) Å, the Bi–Br distances lie within the 2.649(2)–3.246(2) Å range, and the Sb(1)···Br(7) distance is equal to 3.934(2) Å.     

Synthesis and Structure of Triphenylantimony Bis(Acetophenoneoximate)

Triphenylantimony bis(acetophenoneoximate) was synthesized by the reaction of triphenylantimony with hydrogen peroxide in the presence of acetophenone oxime (taken in the molar ratio of 1 : 1 : 2) in ether. The structure of the obtained compound was determined by X-ray diffraction. The Sb atom has a distorted trigonal-bipyramidal coordination with the oxime groups in the axial positions. The Sb–C(Ph)_eq bond lengths are 2.110(1)–2.113(1) Å, and the Sb–O distances are 2.058(1) and 2.067(1) Å. The intramolecular Sb(1)···N(1, 2) contacts and O(1)SbO(2) axial angle are 2.990(1), 2.916(1) Å and 172.49(4)°, respectively.     

Triarylantimony Dicaroxylates Ar3Sb[OC(O)R]2 (Ar = Ph,p-Tol; R = 2-C4H3O, 3-C5H4N): Synthesis and Structure

Bis(2-furoinate)triphenyl- and tri-p-tolylantimony and bis(3-niacinate)triphenylanitmony were synthesized by reacting triarylantimony (Ar₃Sb; Ar = Ph, p-Tol) with 2-furancarboxylic and 3-pyridinecarboxylic acids in the presence of hydrogen peroxide. According to X-ray diffraction data, Sb atoms have trigonal bipyramidal coordination polyhedra. The Sb–O distances are 2.117(4), 2.137(4) Å; 2.136(2), 2.158(2) Å, and 2.112(1), 2.101(2) Å, the Sb···O distances are 2.866(4), 2.798(4) Å; 2.816(2), 2.774(2) Å, and 3.054(2), 3.168(2) Å, respectively.     

Synthesis and Structures of New Enaminones

Two isomeric enaminones were obtained by reaction of ethyl 2-hydroxy-4-(4-hydroxy-6-methyl2H-pyran-2-on-3-yl)-4-oxo-2-butenoate (1) and amines (aniline, benzylamine, butylamine and tyramine) in ethanol. The structures of isomers were studied by ¹³C and ¹H NMR spectra, whereas in the case of isomers 2b, 3a, and 4a (Scheme 1), the crystal structures have been determined by single crystal X-ray diffractometry. The compounds 2b and 3a exist in the solid state as N–C=C–C=O, whereas 4a is in the N–C=C–C–OH tautomeric form (Scheme 2, form A and B, respectively). All three structures exhibit very short intramolecular hydrogen bonds of O–H···O [in the range 2.396(3) – 2.448(3) Å] and N–H···O [in the range 2.580(5) – 2.679(3) Å] type, that are reinforced by delocalization. The crystal structures are in addition stabilized by C–H···O weak hydrogen bonds. In 2b and 3a, the discrete dimers are formed by eight-membered ring containing hydrogen bonds; in 4a, the infinite chains along [1 0 1] direction are formed.     

Synthesis and Structure of Bis(2,4,6-Tribromophenoxy)triphenylantimony

Bis(2,4,6-tribromophenoxy)triphenylantimony was synthesized by reacting triphenylstibine with 2,4,6-tribromophenol in ether in the presence of hydrogen peroxide. Its structure was determined by X-ray diffraction analysis. The coordination polyhedron of the Sb atom is a distorted trigonal bipyramid with the aroxy groups in the axial positions. The bond lengths are Sb(1)–C(Ph) 2.095(4)–2.106(4) Å and Sb(1)–O(1,2) 2.099(3) and 2.092(3) Å. The value of the O(1)SbO(2) axial angle is 177.3(1)°.     

Synthesis and Structure of Tetraphenylantimony 2-Furoinate and Benzoate

Tetraphenylantimony 2-furoinate Ph₄SbOC(O)C₄H₃O is synthesized by the reaction of pentaphenyl-antimony with triphenylantimony bis(2-furoinate). The structure of the compound is determined by X-ray diffraction analysis. The Sb atom in the compound has a distorted trigonal-bipyramidal coordination with the phenyl and 2-furoinate groups in the axial positions. The Sb(1)–C(Ph)_eq distances lie in the 2.119(1)–2.121(1) Å interval; the Sb–O(1) and Sb–C(Ph)_ax bond lengths are equal to 2.273(1) and 2.161(1) Å, respectively; and the Sb(1)···(2) intramolecular contact is 3.234(1) Å.     

Synthesis and Structure of Tetra- and Triphenylantimony Organosulfonates

Tetraphenylantimony 2-naphthalenesulfonate (I), tetraphenylantimony phenylmethanesulfonate (II), and bis(tetraphenylantimony) sulfate (III) were synthesized via reaction of pentaphenylantimony with 2-naphthalenesulfonic acid, triphenylantimony bis(phenylmethanesulfonate), and triphenylantimony sulfate, respectively, in toluene. Triphenylantimony bis(phenylmethanesulfonate) (IV) was synthesized from triphenylstibine, phenylmethanesulfonic acid, and hydrogen peroxide (taken in the molar ratio of 1 : 2 : 1). Organoantimony betaine (V) was obtained by reacting triphenylstibine with phenylmethanesulfonyl chloride in the presence of hydrogen peroxide. The structures of the compounds synthesized were determined using X-ray diffraction analysis. The Sb atoms in I–IV have distorted trigonal bipyramidal coordination. The Sb–C and Sb–O distances are equal to 2.100(4)–2.140(3) and 2.644(2) Å in molecule I, 2.105(2)–2.131(2) and 2.699(1) Å in II, 2.096(6)–2.169(6) and 2.101(6), 2.271(3) Å in III, and 2.101(3)–2.102(5) and 2.111(2) Å in IV. In V, the Sb atoms have close tetrahedral (2.105–2.115 Å) and remote (2.65, 3.019 Å) octahedral environment (the oxygen atoms of sulfo group of their own and neighboring molecules). Two betaine molecules are joined through the O atoms of the sulfo groups of bidentate phenylmethanesulfonate ligands to form a centrosymmetrical dimer. The intermolecular C(1)–H(1)···O(1) hydrogen bonds (3.10 Å) are formed that strengthen the dimer.     

Synthesis and Structure of μ-Peroxo-bis(4-bromophenoxotri-p-tolylantimony)

-Peroxo-bis(4-bromophenoxotri-p-tolylantimony) was synthesized by reacting 4-bromophenol with tri-p-tolylstibine in the presence of hydrogen peroxide. According to X-ray diffraction data, the Sb atoms have trigonal bipyramidal coordination. In the centrosymmetric molecule, the two Sb atoms are joined via bridging peroxo group disordered over two sites. The Sb–O(1,2') bond lengths are equal to 1.999(6) and 2.03(1) Å, the Sb···O(2,1') distances are equal to 2.605(9) and 2.626(5) Å, respectively. The lengths of the terminal Sb–O(3) bonds are 2.093(3) Å.     

Copper(II) Cyanoacetate Polymer: Synthesis and Structure

A new copper carboxylate polymer with cyanoacetate anion as a ligand was synthesized and studied using X-ray diffraction, IR, and EPR spectroscopy. The crystal is tetragonal: a= 14.702(2) Å, c= 13.470(3) Å, Z= 8, space group I4₁/a, and R= 0.0634. The copper atoms in the centrosymmetric dimeric fragment have a square-pyramidal surrounding with the CuO₄N coordination core and are joined through four bidentate bridging anions of cyanoacetic acid Cu(1)"–O(1A) 1.931(4) Å, Cu(1)"–O(1B) 1.926(4) Å, Cu(1)–O(2B) 2.018(3) Å, Cu(1)–O(2A) 2.036(4) Å, and Cu(1)–N(1A)" 2.206(5) Å). The Cu···Cu" distance in the dimer is 2.709 Å. The copper atom is extended from the mean equatorial plane toward the axial nitrogen atom by 0.23 Å. EPR data confirm strong antiferromagnetic interaction (2J –275 cm^–1) between the copper(II) ions of the dimeric fragment, whereas the interaction between the dimers is significantly weaker (J< 0.3 cm^–1).     

Synthesis and Structure of Catena-[Bis(2-Methylimidazole)(μ-Phthalato)cobaltate(II)]

A new coordination compound [Co(Pht)(2-MeIm)₂] (I), where Pht^2–is the deprotonated radical of o-phthalic acid (H₂Pht) and 2-MeIm is 2-methylimidazole, was synthesized. Its structure was established using X-ray diffraction analysis. The crystal is orthorhombic: space group Pca2₁, a= 15.350(3), b= 7.957(2), c= 13.997(3) Å, (calcd.) = 1.505 g/cm³, and Z= 4. The tetrahedral coordination of the Co(II) atom includes two N atoms of two 2-methylimidazole molecules and two oxygen atoms of two carboxyl groups from different acid radicals. The Co–N distances are equal to 2.022(2) and 2.031(2) Å, while the Co–O distances are 1.972(2) and 2.000(2) Å. The carboxyl groups of the Pht^2–radical and the aromatic nucleus form angles of 47.2° and 35.9°, whereas the angle formed by the carboxyl groups themselves is 50.3°. Compound Iis a polymer, which is confirmed by the 1,6-bridging function of the o-phthalic acid radical. The Co···Co distance in a chain is equal to 7.367 Å. Separate chains are united in the crystal into a framework via N–H···O hydrogen bonds.     

Crown ether adducts of olefin complexes of Zeise's salt type – [K(18-crown-6)][PtCl3(olefin)]

[K(18-cr-6)]2[Pt2Cl6] reacts with olefins in CH2Cl2 to give crown ether adducts of olefin complexes of Zeise's salt type [K(18-cr- 6)][PtCl3(olefin)] (2) [olefin: EtCH=CH2 (2a), cis-MeCH=CHMe (2b), trans-MeCH=CHMe (2c), nPrCH=CH2 (2d), cis-EtCH=CHMe (2e), trans-EtCH=CHMe (2f), nBuCH=CH2 (2g), cis-nPrCH=CH-Me (2h), cis-EtCH=CHEt (2i), trans-EtCH=CHEt (2j), cyclohexene (2k), PhCH=CH2 (2l)]. The complexes were characterized by microanalysis, n.m.r. (1H, 13C) and i.r. spectroscopy. The crystal structures of the cis-but-2-ene (2b) and cis-pent-2-ene complexes (2e) were determined by single-crystal X-ray analyses. The Pt atom is square-planar, coordinated by three chloro ligands and the olefin ligand [interplanar angle PtCl3/Pt(C=C) 89.6° (2b), 86.6° (2e)]. The C=C bond length is 1.38(1)Å (2b) and 1.32(2)Å (2e), respectively. The substituents (Me, Et) on the double bond are bent back away from Pt [torsion angles C–C=C–Pt 109(2)–110.7(8)°]. There are close contacts of the [K(18- cr-6)]+ cations both to the trans and one of the cis chloro ligands [K···Cl 3.208(2)/3.230(2)Å (2b); 3.220(5)/3.370(5)Å (2e)].     

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.     

Synthesis and Structure of Triphenylbismuth Difluoride

The reaction of triphenylbismuth dichloride with sodium fluoride in acetone leads to formation of triphenylbismuth difluoride in 73% yield. The X-ray diffraction data show that the bismuth atom in the two symmetrically independent molecules of bismuth difluoride has a trigonal-bipyramidal coordination with equatorial fluorine atoms. The Bi-F and Bi-C distances are 2.53(1)-2.59(1) and 2.10(3)-2.22(2) Å, respectively, and the FBiF angle is 175.1(5)°.     

Intramolecular Hypervalent X←X Interaction in Heteropentalene Compounds Containing S and O Atoms

Chalcogen-containing heteropentalene and quasimonocyclic compounds having O–O–O and S–S–S triads or O–O and S–S diads were studied by the ab initio [MP2(full)/6-31G** and MP2(fc)/ 6-31+G**] and DFT (B3LYP/6-31G**) methods. The oxygen-containing compounds are characterized by strong O···O repulsion which destabilize the pentalene structure. The molecule of 3-thioxo-1-propenesulfenyl fluoride, in contrast to 3-mercapto-2-propenethial, is more stable in the cis-s-cis conformation with an appreciably shortened S–S contact [2.274 Å (MP2), 2.503 Å (B3LYP)] which approaches the length of a standard S–S covalent bond.     

Synthesis and Structure of Tetraphenylantimony Nitrite

Tetraphenylantimony nitrite was synthesized by reacting pentaphenylantimony with triphenylantimony dinitrite at a molar ratio of 1 : 1 in toluene, and its structure was determined using X-ray diffraction analysis. The Sb atom is coordinated to the oxygen atom of the axial nitrite group to form a trigonal bipyramid. The Sb–C(Ph)_eq distances vary within the 2.103–2.111(3) Å range, and the S–O(1) and Sb–C(41) bond lengths are equal to 2.386(3) and 2.156(3) Å, respectively. The Sb...N distance and the axial C(41)SbO(1) angle are equal to 3.133(4) Å and 174.7(1)°, respectively.