Triphenylbismuth bis(3,4-dimethylbenzenesulfonate): Synthesis and structure

Triphenylbismuth bis(3,4-dimethylbenzenesulfonate) Ph₃Bi(OSO₂C₆H₃Me_2-3,4)₂ (I) has been synthesized by the reaction between triphenylbismuth and 3,4-dimethylbenzenesulfonic acid in the presence of tert-butylhydroperoxide (1: 2: 1 mol) in ether. The bismuth atom in complex I has a trigonal bipyramidal coordination to arenesulfonates substituents in axial positions (axial OBiO angle, 173.99(8)°; equatorial CBiC angles, 106.94(11)°, 112.24(11)°, 140.77(11)°). The Bi?C distances are 2.189(3), 2.192(3), and 2.197(3) Å; the Bi?O distances are 2.284(2) and 2.301(2) Å. Some intramolecular contacts are observed between the central atom and the oxygen atoms of sulfonate groups at the maximum equatorial angle (Bi···O 3.122(3), 3.189(4) Å).     

Preparation and x-ray crystal structure of racemic bis(ethylfumarate)bis(acetonitrile)cobalt(0)

The preparation and properties of some new tetracoordinated cobalt(0) complexes containing nitrile and fumaric ester ligands are described. One of them, Co(C₂H₅OOCCHCHCOOC₂H₅)₂(CH₃CN)₂, (la), reacts with 1,10-phenanthroline to give new pentacoordinated and hexacoordinated cobalt(0) complexes.The structure of Ia has been determined from X-ray diffractometer data. The structure was solved by Patterson and Fourier methods and refined by least square techniques to R  0.060 for 2215 independent reflections. Crystals are triclinic, space group P$\text{1}$, with Z  2 in a unit cell of dimensions: a 14.794(18), b 9.448(11), c 10.125(12) Å, α 108.55(9), β 111.42(11), γ 84.95(18)°. The metal is linked to the four carbon atoms of the CHCH groups of the ethyl fumarate residues and to the nitrogen atoms of the two acetonitrile ligands. The coordination of the four ligands around the cobalt atom corresponds to a distorted trigonal pyramid. The four asymmetric carbon atoms of a molecule have the same absolute configuration. RRRR and SSSS molecules are present in the unit cell.     

Kinetics of the polycondensation and copolycondensation of bis(3‐hydroxypropyl) terephthalate and bis(4‐hydroxybutyl) terephthalate

The kinetics of the polycondensation and copolycondensation reactions of bis(3‐hydroxypropyl) terephthalate (BHPT) and bis(4‐hydroxybutyl) terephthalate (BHBT) as monomers were investigated at 270 °C in the presence of titanium tetrabutoxide as a catalyst. BHPT was prepared by the ester interchange reaction of dimethyl terephthalate and 1,3‐propanediol (1,3‐PD). Through the same method adopted for BHPT synthesis, BHBT was prepared with 1,4‐butanediol instead of 1,3‐PD. With second‐order kinetics applied for polycondensation, the rate constants of the polycondensation of BHPT and BHBT, k₁₁ and k₂₂, were calculated to be 4.08 and 4.18 min^?1, respectively. The rate constants of the cross reactions in the copolycondensation of BHPT and BHBT, k₁₂ and k₂₁, were calculated with results obtained from proton nuclear magnetic resonance spectroscopy analysis. The rate constants during the copolycondensation of BHPT and BHBT at 270 °C decreased in the order k₁₂ > k₂₂ > k₁₁ > k₂₁, indicating that the reactivity of BHBT was larger than that of BHPT at 270 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2435–2441, 2002     

The crystal and molecular structures of bis (pentafluorophenyl)disulphide and bis(pentafluorophenyl)diselenide

The structures of (C₆F₅)₂S₂ and (C₆F₅)₂Se₂ have been determined by single crystal, X-ray diffraction techniques. The compounds are isostructural although the molecules are packed differently in the crystal in comparison with their phenyl analogues. Important bond lengths and angles are: SS, 2.059(4)Å; SeSe, 2.319(4)Å; SC, 1.770Å; SeC, 1.910(15)Å; SSC, 101.3(3)°; SeSeC, 98.8(1)°.     

The crystal and molecular structure of dioxo bis (2,2,6,6 - tetramethylheptane -3,5 dionato)methanol uranium (VI)

UO₂(thd)₂ CH₃OH (thd = tetramethylheptane-3,5-dione) is monoclinic, with a = 10.602(11), b = 22.883(20), c = 12.054(11) Å and β = 105.90(3)°, Z = 4 and space group P2₁/c. The structure, which is molecular, was solved by conventional Patterson and Fourier techniques with 3173 independent (hkl) reflexions collected with MoKα radiation (λ = 0.7107 Å), and refined to R = σ(|Fo|-|Fc|)/σ|Fo| = 0.093. The uranium coordination polyhedron is a pentagonal bipyramid, with UO (carbonyl) distances between 2.25 and 2.37 Å and a longer UO (methanol) distance of 2.50 Å. The uranyl group is linear (uranyl angle 179.3(8)°). The pentagon oxygen atoms and uranium do not form a planar system, as there are deviations of up to 0.17 Å from the mean plane. If the methanol oxygen atom O(7) is excluded from the plane calculation, the remaining atoms are more nearly planar. The four carbonyl oxygens are coplanar, with uranium 0.08 Å from their plane. The methanol oxygen is 0.28(4) Å from this second plane.The two (thd) molecules, excluding methyl carbons, are planar and are inclined at 43.6° to each other in a boat form and at 29.1 and 14.5° to the pentagonal plane. The methanol CO bond is inclined at 133° to the UO bond, confirming the ligand is the neutral CH₃OH molecule, and not CHO^?₃.     

Darstellung und eigenschaften von bis(μ-fumarato)bis[di(π-cyclopentadienyl)titan(IV)]; strukturuntersuchungen der reinen und der kristall-chloroform enthaltenden phase

The reaction of titanocene dichloride with disodium fumarate in the two-phase system H₂O/CHCl₃ yields bis(μ-fumarato)bis[di(π-cyclopentadienyl)titamum(IV)]. Crystal data for the pure compound (IIIa): monoclinic, P2₁/n, a 18.558(5), b 9.076(5), c 7.559(2) Å, β 101.69(2)°; Z = 2. Crystal data for a phase containing chloroform of crystallization (CHCl₃/Ti = $\text{1}\text{1}$) (IIIb): triclinic, P$\text{1}$, a 20.439(11), b 10.269(5), c 8.858(3) Å, α 112.18(3), β 93.93(5), γ 91.63(7)°; Z = 2 × 1. The three independent [(π-C₅H₅)₂TiOCOCHHOCO]₂ molecules differ in the puckering of their 14-membered rings and the geometry of their TiOC units.     

Kinetic study on the ligand exchange reactions between bis(alkylxanthato)palladium(II)and bis(N,N-dialkyldithiocarbamato)palladium(II)by high-performance liquid chromatography

The rate constants and equilibrium constants of ligand exchange reactions between his(alkylxanthato)palladium(Ⅱ),Pd(S_2COR)_2(R=Am,n-Hex,Bz),and bis(N,N-dialkyldithiocarbamato)palladium(Ⅱ),Pd(S_2CNR_2)_2(K=Et,n-Pr,n-Bu),in chloroform solution have been determined ina temperature range of 20—50°C by means of high-performance liquid chromatography.It was foundthat both the forward and reverse reactions are of second order.All of the equilibrium constants Kdetermined are 10.3±1.0,much greater than the value(K=4)calculated statistically which indicatesthat the ternary complexes are more stable than the binary complexes.The experimental resultsrevealed that the reaction rate decreases with the increase in the size of R and R~1 groups and the latterare more remarkable,consistent with the deduction of steric effect.The activation parameters ofthe reactions have been calculated.In reaction series(11)and(12)(in the text)the isokinetic tempera-tures B=390±8K and β=346±15 K have been observed respectively.A plausiblemechanism in-volving an eight-membered ring intermediate has been proposed on the basis of experimental results.     

The spectroscopic and structural characterization of trans-hydrido(1,1-dimethylallene(bis(tricyclohexylphosphine)platinum(II) hexafluorophosphate

The platinum hydride cation, trans-[PtH(CH₃OH)(P(C₆H₁₁)₃)₂]⁺ reacts with 1,1-dimethylallene at room temperature in dichloromethane to lose methanol and form an allene complex which has been characterized by ¹H NMR spectroscopy and X-ray diffraction. Crystals grown from a mixture of hexane and o-dichlorobenzene are monoclinic, space group P2₁/n, with cell dimensions a 14.807(2), b 29.404(7), c 11.621(2) Å and β 90.75(1)°. There are four units of trans-[PtH(C₅H₈)(P(C₆H₁₁)₃)₂]PF₆, C₆H₄Cl₂ in the cell. Three dimensional X-ray data collected by diffractometer techniques have permitted full matrix least-squares refinement to a conventional agreement factor R = 0.052. The platinum atom has a square planar coordination geometry, with the planar allene ligand bonded at an angle of 89.2(6)° to the coordination plane, and PtC distances of 2.305(10) and 2.233(10) Å.     

A thermal behaviour and structural study of bis(hydroxamato)oxovanadium(IV) complexes

The bis(hydroxamato)oxovanadium(IV) complexes of composition [VO(IAH)₂)] (I), [VO(IBH)₂)] (II) and [VO(ICH)₂)] (III) (where IAH = indole-3-acetohydroxamate; (C₉H₈NCONHO^?); IBH = indole-3-butyrohydroxamate; (C₁₁H₁₂NCONHO^?); ICH = indole-2-carbohydroxamate; (C₈H₆NCONHO^?)) synthesized form the reactions of VOSO₄·5H₂O with bi-molar amounts of potassium salts of the respective hydroxamic acids in methanol have been characterised by elemental analyses, magnetic moment measurements and IR spectral studies. The thermal behaviour of complexes has been studied by TG and DTA techniques. Thermograms indicated that all complexes decompose in two steps yielding [VO(IAH)], [VO(IBH)] and [VO(ICH)] as intermediate of respective complexes and VO₂ as the final product of decomposition in each case. From the initial decomposition temperatures (IDT), the order of thermal stability for the complexes has been inferred as II > I > III.     

Carbonylierung von bis(triphenylphosphin)-platin(II)- und -palladium(II)-komplexen in gegenwart von aminen und α-aminosäureestern

The crystal structure of (C₅H₅)₃Pr·CNC₆H₁₁ was determined from single-crystal X-ray diffraction data. The monoclinic unit cell of dimensions a = 8.298(3), b = 21.66(1), c = 11.943(4) Å, and β = 104.98(3)° contains four molecules in general positions of space group P2₁/c. Each molecule is composed of three C₅H₅ rings in a nearly exact trigonal array, η⁵-bonded to the Pr atom at a distance of 2.53 Å to the centroid of each ring, plus a single CNC₆H₁₁ adduct attached to the Pr atom along the trigonal axis at 2.65 Å. The presence of a CN triple bond in the isonitrile moiety and the nearly linear CNC configuration add credence to the previous proposal that there is a pure donor bond from the isonitrile carbon to the metal atom.     

The polysulfonylamines bis(methylsulfonamido) sulfone and bis(trifluoromethylsulfonamido) sulfone

Bis­(methyl­sulfon­amido) sulfone, C₂H₈N₂O₆S₃ or SO₂(NHSO₂CH₃)₂, was synthesized from imidobis­(sulfonyl ­chloride), HN(SO₂Cl)₂, and bis­(tri­methyl­silyl)­methane, CH₂[Si(CH₃)₃]₂, in ­chlorotri­methyl­silane solution. In the solid state, there are two independent mol­ecules linked by two N—H⋯O hydrogen bridges into infinite chains parallel to the b axis. The central S atoms of the independent molecules each lie on a twofold axis. Bis­(tri­fluoro­methyl­sulf­onamido) sulfone, C₂H₂F₆N₂O₆S₃ or SO₂(NHSO₂CF₃)₂, was formed by the reaction of tri­chloro­phosphazosulfuryl tri­fluoro­methane, Cl₃PNSO₂CF₃, with fluoro­sulfonic acid, FSO₃H. The mol­ecules are connected by bifurcated N—H⋯O bridges into infinite layers parallel to the [001] plane. The central S atom lies on a twofold axis.     

Hexaaquacobalt(II) bis[hydrogen bis(4‐carboxyphenylphosphonate)] dihydrate

The Co^II ion in the title complex salt, [Co(H₂O)₆](C₁₄H₁₃O₁₀P₂)₂·2H₂O or [Co(H₂O)₆][H(C₇H₆O₅P)₂]·2H₂O, resides on an inversion centre and exhibits an octahedral environment formed by six aqua ligands. Two unique acid residues share an H atom between their phosphonate groups, forming a complex monoanion with a very short (P)O...H...O(P) hydrogen bond of 2.435 (2) Å. The crystal structure is layered and consists of thick organic bilayers with hydrated metal [Co(H₂O)₆]²⁺ ions arranged between them. The interior of the bilayer is occupied by the aromatic portions of the complex monoanions and the carboxyl groups, which form hydrogen‐bonded R₂²(8) ring motifs. The phosphonate groups are arranged outwards in order to form the hydrogen‐bonded surfaces of the bilayer. Electrostatic and multiple hydrogen‐bond interactions, established between the coordination and solvent water molecules and the phosphonate O atoms, hold neighbouring bilayers together.     

Two new polymorphs of trans‐bis(hinokitiolato)copper(II)

The title complex [systematic name: trans‐bis(3‐iso­propyl‐7‐oxo­cyclo­hepta‐1,3,5‐trienolato)copper(II)], [Cu(C₁₀H₁₁O₂)₂],is a substance possessing antimicrobial activity. The compound crystallizes in a number of polymorphic forms, the structures for two of which are reported here. Stacks of square‐planar mol­ecules exhibiting weak intermolecular copper–olefin π interactions (not observed in earlier reports on this substance) are described. The mol­ecules have crystallographically imposed inversion symmetry, with stacking and copper–olefin π distances ranging from 3.226 (2) to 3.336 (1) Å.     

Hydrogen‐bonded bilayers in ­piperazinium(2+) bis(mandelate) bis(methanol) solvate

In the title compound, C₄H₁₂N₂²⁺·2C₈H₇O₃^?·2CH₄O, the cations lie across centres of inversion and are disordered over two orientations with equal occupancy; there are equal numbers of (R)‐ and (S)‐mandelate anions present (mandelate is α‐hydroxy­benzene­acetate). The anions and the neutral water mol­ecules are linked by O—H?O hydrogen bonds [O?O 2.658 (3) and 2.682 (3) Å, and O—H?O 176 and 166°] into deeply folded zigzag chains. Each orientation of the cation forms two symmetry‐related two‐centre N—H?O hydrogen bonds [N?O 2.588 (4) and 2.678 (4) Å, and N—H?O 177 and 171°] and two asymmetric, but planar, three‐centre N—H?(O)₂ hydrogen bonds [N?O 2.686 (4)–3.137 (4) Å and N—H?O 137–147°], and by means of these the cations link the anion/water chains into bilayers.     

Polymeric bis[bis(2,2′-bipyridine)­nickel(II)] hexavanadate(V)

The structure of the title compound, μ-hexavanadato(V)-bis­[bis(2,2′-bi­pyridine)­nickel(II)], [{Ni(C₁₀H₈N₂)₂}₂{V₆O₁₇}], is composed of vanadium oxide layers intercalated by complex [Ni(bipy)₂]²⁺ cations (bipy is 2,2′-bi­pyridine). The structure is isomorphous with that reported recently for [Zn(bipy)₂]₂[V₆O₁₇] [Zhang, DeBord, O'Connor, Haushalter, Clearfield & Zubieta (1996). Angew. Chem. Int. Ed. Engl. 35 , 989–991]. The vanadium oxide layers are built up solely from VO₄ tetrahedra by corner sharing and clearly exhibit a sinusoidal ruffling. Two O atoms from a single vanadium oxide layer are coordinated to each Ni atom of the complex cations in a cis fashion, with Ni—O distances of 2.027 (3) and 2.087 (3) Å, thus maintaining the two-dimensional structure.     

Homogene katalytische hydrierung mit IrCl(CO)L2 bei mittleren aktivitäten bis 180 und umsatzzahlen bis 150 000

Homogeneous hydrogenation without solvent of unsaturated compounds with IrCl(CO)L₂ as catalyst was examined as a function of ligand L, temperature and mmol catalyst employed. Best results were found with the ligand P(C₆H₁₁)₃ in the temperature range 80 to 120°C and 10 atm H₂ pressure. Mean activities ā up to 180 and turnover numbers UZ up to 150.000 were found.     

Novel materials from bis(arene)metal‐containing polyacrylonitrile

Novel bis(arene)metal‐containing polyacrylonitrile materials have been prepared by the polycyanoethylation reaction between acrylonitrile and (arene)₂M (M = Cr or V; arene = PhH, C₆H₄Et₂ or mesitylene) in the absence of solvent. The resulting star‐shaped molecules consist of a central (arene)₂M species with up to four polyacrylonitrile arms covalently bonded to the arene ligands. The materials are readily soluble and films can be cast from solutions in acetonitrile. The IR and solid state ¹³C NMR spectra (or EPR spectrum for the oxidized chromium‐containing polymer) are consistent with the presence of a metal–arene bond and confirm the persistence of the sandwich structure. The properties of the thermolysed materials are consistent with the formation of conjugated naphthyridine‐type structures. The value of |n₂| determined by the degenerate four‐wave mixing technique at 1064 nm with a 6 ns pulse duration for a solution in conc. H₂SO₄ (1 g l⁻¹) of the chromium‐containing polymer pyrolysed at 350 °C was found to be 0.8 × 10⁻¹³ cm² W⁻¹ corresponding to |lRe _χ⁽³⁾| = 0.4 × 10⁻¹¹ esu.     

μ‐Oxo‐bis[(η5‐1,2‐dicarbaundecabor­ato)bis(N,N‐dimethylacetamidinato)tantalum] dichloromethane hemisolvate

The structure of the title compound, [Ta₂O(C₂B₉H₁₁)₂(C₄H₉­N₂)₄]·0.5CH₂Cl₂, contains two (C₂B₉H₁₁)Ta[NC(Me)NMe₂]₂ units bridged by a nearly linear [Ta—O—Ta 163.4 (4)°] μ‐oxo ligand. The dichloromethane molecule lies on a twofold axis.     

trans‐Bis(hinokitiolato)copper(II) trans‐bis(hinokitiolato)palladium(II) cocrystals with (5/1) and (3/2) formulations

trans‐Bis(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)copper(II) trans‐bis(3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olato)palladium(II) as the (5/1) and (3/2) composites [Cu(C₁₀H₁₁O₂)₂]·0.2[Pd(C₁₀H₁₁O₂)₂] and [Cu(C₁₀H₁₁O₂)₂]·0.67[Pd(C₁₀H₁₁O₂)₂], respectively, where 3‐isopropyl‐7‐oxocyclohepta‐1,3,5‐trien‐1‐olate is the systematic name for the hinokitiolate anion (hino), are the first mixed‐metal cocrystalline products isolated from the M_x(hino)_y family of complexes. These cocrystals contain square‐planar trans‐Cu(hino)₂ and trans‐Pd(hino)₂ molecules possessing crystallographic inversion symmetry. The bulk formulation for these cocrystalline compounds is Cu_1−xPd_x(hino)₂, where x is 0.166 (4) for the (5/1) product and 0.399 (4) for the (3/2) product. This bulk formulation is simply a convenient average expression of the whole‐molecule substitutional disorder present in these compounds. The M—O bonds are in the range 1.9210 (11)–1.9453 (10) Å, the O—M—O bite angles are in the range 82.94 (4)–83.36 (4)°, and all of the hinokitiolate O atoms are involved in C—H...O hydrogen‐bonding interactions.