π-Olefin-iridium-komplexe : IV. Umsetzungen von chloro-dien-iridium-verbindungen mit lithiumorganylen

The complexes [(1,3-C₆H₈)₂IrR] and [(1,3-C₇H₁₀)₂IrR] (R = CH₃, C₆H₅) are obtained by reaction of the corresponding chloro compounds with RLi. Interaction of [Ir(COD)Cl]₂ (COD = 1,5-cyclooctadiene) with CH₃Li in the presence of 1,3-cyclohexadiene or isoprene yields [(COD)(1,3-C₆H₈IrCH₃] and [(COD)(C₅H₈IrCH₃], respectively. The products of the reaction of chlorodicyclodieneiridium with n-C₄H₉Li depend on the ring size of the cyclodiene ligands; with 1,3-cyclohexadiene [(1,3-C₆H₈)₂IrH] is formed while with 1,3-cycloheptadiene [(1,3-C₇H₁₀)(C₇H₉)Ir] is obtained together with [(1,3-C₇H₁₀)₃Ir₂(μ-H)₂]. Chemical and spectroscopic properties of the new compounds are discussed.     

π-Olefin-iridium-komplexe : II. Synthese und dynamisches verhalten von bis(η4-Cyclodien)-hydrido-iridium(I)-komplexen

By reaction of [Ir(COD)Cl]₂ (COD = 1,5-cyclooctadiene) with i-C₃H₇MgBr in the presence of cyclic dienes, complexes of the type [IrH(COD)L] (L = 1,3-cyclohexadiene, 2-methyl-],3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene) are obtained. The system IrCl₃/i-C₃H₇MgBr/1,3-C₆H₈ yields [IrH(1,3-C₆H₈)₂]. According to NMR spectroscopic investigations the pure hydrido forms exist in solution only at low temperatures while at room temperature dynamic H-addition—elimination equilibria of the type [IrH(η⁴-diene)(COD)] ? [Ir(η³-enyl)(COD)] and [IrH(η⁴-1,3-C₆H₈)₂] ? [Ir(η³-C₆H₉)-(η⁴-1,3-C₆H₈)], respectively, are observed; the hydrogen at the iridium atom is thereby transferred to the endo positions of the diene ligands.     

Shock tube and modeling study of 1,3-butadiene pyrolysis

1,3-Butadiene (1,3-C₄H₆) was heated behind reflected shock waves over the temperature range of 1200–1700 K and the total density range of 1.3 × 10⁻⁵ −2.9 × 10⁻⁵ mol/cm³. Reaction products were analyzed by gas-chromatography. The concentration change of 1,3-butadiene was followed by UV kinetic absorption spectroscopy at 230 nm and by quadrupole mass spectrometry. The major products were C₂H₂, C₂H_4, C₄H₄, and CH₄. The yield of CH₄ for a 0.5% 1,3-C₄H₆ in Ar mixture was more than 10% of the initial 1.3-C₄H₆ concentration above 1500 K. In order to interpret the formation of CH₄ successfully, it was necessary to include the isomerization of 1,3-C₄H₆ to 1,2-butadiene (1,2-C₄H₆) and to include subsequent decomposition of the 1,2-C₄H₆ to C₃H₃ and CH₃. The present data and other shock tube data reported over a wide pressure range were qualitatively modeled with a 89 reaction mechanism, which included the isomerizations of 1,3-C₄H₆ to 1,2-C₄H₆ and 2-butyne (2-C₄H₆). © 1996 John Wiley & Sons, Inc.     

A polyoxoniobate constructed from Lindqvist-type hexaniobates and copper coordinated cations

A new organic–inorganic hybrid polyoxoniobate [Cu(1,3-dap)₂(H₂O)][(H₆Nb₆O₁₉)₂Cu(1,3-dap)₂]?·?4(1,3-dap)·20H₂O (1) (1,3-dap?=?1,3-diaminopropane) has been synthesized by the diffusion method and structurally characterized by elemental analyses, infrared spectrum, ultraviolet spectroscopy, and single crystal X-ray diffraction. Crystal structure analysis reveals that 1 consists of a dimeric dumbbell anion [(H₆Nb₆O₁₉)₂Cu(1,3-dap)₂]^2?, a copper coordinated cation, four 1,3-dap ligands and 20 crystal water molecules. Neighboring units are combined via hydrogen bonds forming a 3-D supramolecular framework.     

Reactions of alkylcobalt complexes containing a tetradentate nitrogen-donating ligand

The reactions of RCo(BDM1,3pn)(H₂O) with light, heat, acids, electrophiles and nucleophiles were studied. (HBDM1,3pn is a mononegative, tetradentate dioxime-diimine ligand formed by condensing 2,3-butanedionemonoxime with 1,3-propanediamine in a 2/1 molar ratio; R = CH₃, C₂H₅, n-C₃H₇, n-C₄H₉, and C₆H₃CH_2-) Pyrolysis and photolysis of the alkyl complexes result in a cobalt(II) complex (anaerobic conditions) along with alkenes and alkanes. The major organic products from solid state pyrolysis at 200°C or photolysis in water are CH₄ (R = CH₃), C₂H₄ (R = C₂H₅), C₃H₆ (R = n-C₃H₇), C₄H₈ (R = n-C₄H₉) and (C₆H₅CH₂)₂ (R = C₆H₅CH₂). No alkyl—cobalt bond cleavage occurs with acids or bases in most cases. Two exceptions are the reactions with 3 M HNO₃ at 25°C and with 1 M NaOH at 52°C. Electrophiles like I₂ cleave the alkyl—cobalt bond forming RI and Co^III (BDM1,3pn)I₂. Nucleophilic reagents (N^-) displace the H₂O trans to the alkyl group to form RCo(BDM1,3pn)(N), but do not dealkylate the alkyl complex under the reaction conditions studied.     

Quantum chemical modeling of the structure formation and proton transfer in 2-hydroxybenzenesulfonic, 4-hydroxy-1,3-benzenedisulfonic, and 1,3-benzenedisulfonic acids

Hydrate clusters of 2-hydroxybenzenesulfonic and 1,3-benzenedisulfonic acids were calculated in terms of the density functional theory (DFT) by the B3LYP/6-31G** method. The process of water adsorption on the crystal surface of 4-hydroxy-1,3-benzenedisulfonic acid dihydrate was simulated using the generalized gradient approximation (DFT/PBE) and periodic boundary conditions. For the model system (OHC₆H₄SO₃ ^?)·H₅O₂ ⁺, the activation barriers for the proton transfer were calculated depending on the distance between the O atoms and the deviation of the proton from the O...O bond line. The presence of one H₂O molecule per SO₃H group is energetically most favorable for the formation of clusters of 1,3-benzenedisulfonic acid containing a stoichiometric amount of water. The simulation of the hydration of 4-hydroxy-1,3-benzenedisulfonic acid dihydrate (OHC₆H₃(SO₃H)₂·2 H₂O + n H₂O, n = 1–3) showed that the superstoichiometric H₂O molecule is adsorbed on the crystal surface of this dihydrate with energy release of 0.75–0.95 eV. The position of this water molecule is less favorable in the bulk than on the surface.     

The complex Eu(phen)L3��5CH2Cl2 (HL is 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)propane-1,3-dione): synthesis, crystal structure, and luminescent properties

A reaction of Eu(NO₃)₃·6H₂O with the novel heterocyclic ligand 1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)propane-1,3-dione and 1,10-phenanthroline in the presence of NaOH gave the complex Eu(phen)L₃·5CH₂Cl₂. The crystal structure of the complex was determined by single-crystal X-ray diffraction. The coordination polyhedron {EuO₆N₂} is a tetragonal antiprism. The complex shows bright orange-red luminescence in both the solid state and solution.     

The mechanism of ethylene pyrolysis at small conversions

Kinetic modelling is used in conjunction with measurements of product yields to develop a mechanism for the pyrolysis of ethylene at 896K and ethylene pressures ranging from approximately 3 to 78 kPa. An induction period was observed for all products except H₂, and was followed by a steady rate, which was of second-order for all products except 1,3-C₄H₆, the most abundant product. The mechanism quantitatively accounts for the yields of H₂, CH₄, C₂H₆, C₃H₆, 1-C₄H₈ and 1,3-C₄H₆. The reaction is initiated by disproportionation of C₂H₄ and the product 1,3-C₄H₆ results from decomposition of the C₄H₇ radical, formed by addition of C₂H₃ to C₂H₄. The other organic products that were measured are formed as a result of reactions involving the C₂H₅ radical. The hydrogen is produced by abstraction from C₂H₄ by atomic hydrogen and its rate is controlled by the reaction C₂H₅ → C₂H₄ + H which is nearly equilibrated. The main termination reaction is recombination of C₂H₅. The auto-acceleration which is evident particularly in the yields of H₂, CH₄, C₂ H₆, and C₃H₆ is accounted for by the decomposition of 1-C₄H₈. © 1996 John Wiley & Sons Inc.     

Synthesis of oxoindolin-3-ylidene-1,3-dithioles

An efficient and one-pot synthesis of 2-(2-oxoindolin-3-ylidene)-1,3-dithiole-4,5-dicarboxylates by a three-component condensation reaction of isatins, carbon disulfide and dialkyl acetylendicarboxylates in the presence of Bu₃P is reported. Reaction of carbon disulfide and dialkyl acetylene dicarboxylates with acenaphthylene-1,2-dione, ninhydrine and pyrimidine-tetraone resulted in the formation of 2-(2-oxoacenaphthylen-1(2H)-ylidene)-1,3-dithiole-4,5-dicarboxylates, 2-(1,3-dioxo-1H-inden-2(3H)-ylidene)-1,3-dithiole-4,5-dicarboxylates and 2-(2,4,6-trioxotetrahydropyrimidin-5(6H)-ylidene)-1,3-dithiole-4,5-dicarboxylates, respectively, in the same conditions.     

A Novel Three-Dimensional Network Isophthalato-Bridged Lanthanide Complex: {Ln[C6H4(COO−)2-1,3](CH3COO−)(H2O)2}·H2O

The three-dimensional network of lanthanide (III) complexes with isophthalato (IPT) ligand, (Eu[C₆H₄(COO^?)₂-1,3](CH₃COO^?)(H₂O)₂}·H₂O 1 and {Sm[C₆H₄(COO^?)₂-1,3](CH₃COO^?) (H₂O)₂} H₂O 2, has been prepared by the hydro(solvo)thermal reaction of Eu(C1O₄)₃·6H₂O or Sm(C1O₄)₃·6H₂O, 1,3-dicyanobenzene and acetic acid in the presence of ethanol and H₂O. In the reaction, 1,3-dicyanobenzene was hydrolyzed to give IPT ligand. Single crystal x-ray analysis revealed that crystals 1 and 2 are isomorphous with the isostructural {M[C₆H₄(COO^?)₂-1,3](CH₃COO^?)(H₂O)₂}·H₂O unit. In 1 and 2, IPT acts as a bridging ligand to connect three adjacent metal atoms, forming a network like an undulating sheet paralleling the bc plane. The carboxylate from acetate bridges two adjacent metal atoms in a tridentate mode between the different sheets to extend the structure into a three-dimensional network.     

β-Tricarbonyl compounds. I. 2,4-Disubstituted 1,3-cyclopentanediones

Summary Stable enolic isomers of 2-aroyl-4-aracyl-1,3-cyclopentanediones such as3 and4 were prepared by condensation of aryl methyl ketones and diethyl maleate using an excess of sodium ethoxide (Aryl=C₆H₅, 4-C₆H₄CH₃, 4-C₆H₄Br and 4-C₆H₄Cl).

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-Tricarbonyl Verbindungen. I. 2,4-Disubstituierte 1,3-Cyclopentandione

Zusammenfassung Stabile Enol-Isomere von 2-Aroyl-4-aracyl-1,3-cyclopentandionen wie3 und4 wurden durch Kondensation von Arylmethylketonen und Diethylmaleat mit einem Überschuß von Natriumethoxid dargestellt (Aryl=C₆H₅, 4-C₆H₄CH₃, 4-C₆H₄Br und 4-C₆H₄Cl).

     

(1,3-Diformylindenyl)cyclopentadienyl ruthenium derivatives

The reaction of [CpRu(CH₃CN)₃][PF₆], [Cp*RuCl] _n , and [Cp^FRuCl]n with 1,3-diformylindene results in the predominant formation of zwitter-ionic arene-cyclopentadienyl complexes {η⁶-1,3-(CHO)₂C₉H₅}RuCp (Cp = C₅H₅), {η⁶-1,3-(CHO)₂C₉H₅}RuCp* (Cp* = C₅Me₅), and {η⁶-1,3-(CHO)₂C₉H₅}RuCp^F (Cp^F = C₅Me₄CF₃), respectively. The ruthenocenes {η⁵-1,3-(CHO)₂C₉H₅}RuCp, {η⁵-1,3-(CHO)₂C₉H₅}RuCp*, and {η⁵-1,3-(CHO)₂C₉H₅}RuCpF were synthesized by the reaction of 1,3-diformylindenyl potassium with [CpRu(CH₃CN)₃][PF₆], [Cp*RuCl] _n , and [Cp^FRuCl] _n .     

Über Oxarsolane und Thioarsolane

Elimination of HCl from 1,3-propanoldichloroarsine, HOC₃H₆AsCl₂, yields 2-chloro-1,2-oxarsolane. Hydrolysis in the presence of triethylamine gives bis-1,2-oxarsolanyloxide. Bis-1,2-thioarsolanyl-sulphide is obtained from 1,3-chloropropyl-arsenicsulphide, (ClC₃H₆AsS)₃, by interaction with thiourea and decomposition of the intermediate thiuronium salt. Reaction with AsCl₃ yields the 2-chloro-1,2-thioarsolane which may be hydrolized to bis-1,2-thioarsolanyl-oxide.     

Zur Kenntnis der Chemie und der Struktur von Olefin-monocyano-dicarbonyl-ferrat-Anionen

About Chemistry and Structure of Olefin-monocyano-dicarbonyl-ferrate Anions By the reactions of olenFe(CO)₃ [olen = C₅H₈(isoprene), C₇H₁₀(cycloheptadiene-1,3), C₈H₁₄(2,5-dimethylhexadiene-1,3)] with sodium bis [trimethylsilyl]amide the new anions [olenFe(CO)₂CN]^? are formed. All so far known [olenFe(CO)₂CN]^? complexes [olen = C₅H₈(isoprene), C₇H₁₀[cycloheptadiene-1,3], C₄H₆(butadiene), C₅H₈(pentadiene-1,3), C₆H₈(cyclohexadine-1,3), C₆H₁₀(2,3-dimethylbutadiene), C₈H₈(cyclooctatetraene)] have fluctional structures in solution as shown by ¹³C NMR spectroscopic investigations. At low temperatures only the isomer exists, in which the CN^? ligand and one of the two CO molecules occuppy the basal positions of a square pyramide together with 2 C atoms of the diene part.     

Synthesis of binuclear rhodacarboranes from 1,4-and 1,3-C6H4(CH2-9-C2H2B9H9-7,8-nido]2 2− dianions and (Ph3P)3RhCl

1,4- and 1,3-C₆H₄(CH₂-9-C₂H₂B₉H₉-7,8-nido]₂ ^2? dianions obtained fromnido-7,8-dicarbollide ion and 1,4-bis(bromomethyl)- and 1,3-bis(bromomethyl)benzenes react with (Ph₃P)₃RhCl to give binuclear rhodacarboranes, 1,4- and 1,3-[3,3-(Ph₃P)₂-3-H-3,1,2-RhC₂B₉H₁₀-4-CH₂]₂C₆H4.     

Aqueous-Mediated green synthesis of novel spiro[indole-quinazoline] derivatives using kit-6 mesoporous silica coated Fe3O4 nanoparticles as catalyst

In this work, a series of eight new spiro[3,4′]1,3-dihydro-2H-indol-2-one-2′-amino-4′,6′,7′,8′-tetrahydro-2′,5’(1’H,3’H)-quinazoline-diones were successfully synthesized through a three-component reaction of 1H-indole-2,3-diones (isatins), guanidine nitrate, and 1,3-cyclohexanediones, by use of Kit-6 mesoporous silica coated Fe₃O₄ nanoparticles (Fe₃O₄@SiO₂@KIT-6) as a highly efficient magnetically separable nanocatalyst in aqueous media at 60°C. Several notable features of thiseco-friendly protocol are high yields of products, short reaction times, operational simplicity, and the use of easily available and recyclable catalyst.     

N-(1,3-Thiazol-5(4H)-yliden)amine aus 1,3-dipolaren Cycloadditionen von Aziden mit 1,3-Thiazol-5(4H)-thionen

N-(1,3-Thiazol-5(4H)-ylidene)amines via 1,3-Dipolar Cycloaddition of Azides and 1,3-Thiazol-5(4H)-thiones Organic azides 5 and 4,4-dimethyl-2-phenyl-1,3-thiazol-5(4H)-thione ( 2 ) in toluene at 90° react to give the corresponding N-(1,3-thiazol-5(4H)-ylidene)amines (= 1,3-thiazol-5(4H)-imines) 6 in good yield (Table). A reaction mechanism for the formation of these scarcely investigated thiazole derivatives is formulated in Scheme 3: 1,3-Dipolar azide cycloaddition onto the C?S group of 2 leads to the 1:1 adduct C . Successive elimination of N₂ and S yields 6 , probably via an intermediate thiaziridine E .     

Two distinct manganese(II) complexes with hexadentate 1,3-propanediaminetetraacetate ligand: The ability of metal(II) complexes with 1,3-pdta ligand to form solid solutions

The ability of Mn(II) ion to form two distinctly different complexes with 1,3-propanediaminetetraacetate (1,3-pdta) ligand has been demonstrated by performing X-ray analyses of their crystalline Mg(II) salts. The two types of Mn(II) complexes have been obtained by different synthetic routes and their crystals constitute, respectively, the solid solution of the composition [Mg(H₂O)₆][Mg_0.5Mn_0.5(1,3-pdta)] · 2H₂O (1) and the ordered crystals of the composition [Mg(H₂O)₆][Mn(1,3-pdta)(H₂O)] · 2H₂O (2). In both, six- 1 and seven-coordinated 2 Mn(II) complexes the 1,3-pdta ligand acts as a hexadentate. As 2 makes the second example of the seven-coordinated 1,3-pdta complex with divalent transition metal ion, the other being the [Mg(H₂O)₆][Cd(1,3-pdta)(H₂O)] · 2H₂O (3) complex, the paper reports the results of X-ray investigations of both of these complexes at 130 K.     

Catalytic Cycloaminomethylation of Aminobenzamides with 1,3-Bis[dimethylamino(methoxy)methyl]thiourea

Efficient methods of the synthesis of cyclophanes containing the thiourea moiety via the reaction of o-, m-, and p-aminobenzamides with 1,3-bis(dimethylaminomethyl)thiourea or 1,3-bis(methoxymethyl)thiourea using NiCl₂·6H₂O and SmCl₃·6H₂O as catalysts have been developed.

     

Azoles and azines

The dipole moments of 2-aryl-4-chloro-6-oxo-1,3-thiazines and 2-aryl-4-chloro-5-formyl-6-oxo-1,3-thiazines (Ar=C₆H₅, C₆H₅Cl-p, C₆H₅CH₃-p) were determined experimentally in benzene and calculated by the additive scheme with the vector method, as well as by the PPDP/2 method. Comparison of the data obtained with the calculated data showed that the formyl group is taken out of the plane of the thiazine ring.For Communication 64, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 272–275, February, 1988.