New substituted titanocene, zirconocene and hafnocene dichlorides

Summary Twentytwo new substituted metallocene Cp¹Cp²MCl₂ (M = Ti, Zr or Hf) dichlorides have been prepared and the catalytic activity of some of them in alkene polymerization has been primarily evaluated.     

苯氧基稀土二氯化合物的合成

Mehrotra 等人曾报道三烷氧基稀土化合物与乙酰氯反应,合成烷氧基稀土一氯或二氯化合物,Misra 等人以三异丙氧基稀土化合物[Ln(OPr-i)_3,Ln=Nd,Pr]与苯酚在苯溶剂中反应,制备了三苯氧基稀土化合物,但有关苯氧基稀土二氯化合物的合成迄今未见报道.     

Synthesis of diferrocenylmethoxyethanol via reaction of diferrocenylmethyl cabonium with glycol and its crystal structure

The new compound diferrocenylmethoxyethanol has been synthesized from the reaction of glycol in the presence of triethylamine with diferrocenylmethyl carbonium which was generated by diferrocenylmethanol treated with BF₃ in CH₂Cl₂ without separation from the reaction mixture. Diferrocenylmethoxyethanol was characterized by elemental analysis, ¹H NMR and IR. The structure was also confirmed by a X-ray single crystal study. It was found that diferrocenylmethoxylethanol crystallized in a monoclinic P2₁ space group and a=5.8250(8) Å, b=7.4034(10) Å, c=21.773(3) Å, α=90°, β=95.020(3)°, γ=90°, V=935.4(2) Å³, Z=2, D _c=1.577 mg·m^?3, μ=1.566 mm^?1, F(0 0 0)=460.     

Synthesis and crystal structure of diferrocenylmethoxyethylamine

The reaction of diethanolamine with diferrocenylmethyl carbonium (2) that was generated by diferrocenylmethanol (1) treated with BF₃ in CH₂Cl₂ provided the synthesis of title compound diferrocenylmethoxyethylamine (3). The structure of 3 was determined by the X-ray diffraction (XRD) with crystal data: monoclinic P2₁/n space group and a=5.8419(14) Å, b=13.572(3) Å, c=23.839(6) Å, α=90°, β=91.827(5)°, γ=90°, V=1889.2(8) Å³, Z=4, D _c =1.558 mg·m^?3, μ=1.548 mm^?1, F(000)=920. The intra- and inter-molecular H bonding modes in 3 were demonstrated both in molecular crystal structure and IR spectral characterization.     

Synthesis and crystal structure of poly-trivinyltinferrocenoate

Binuclear complexes of formula C₅H₁₅FeC₅H₄COOSn(CHCH₂)₃ (I), C₅H₅FeC₅H₄COOSnPh₃ (II) and Ph₃GeCOOSnPh₃ (III) have been prepared and characterized by IR spectra. The polymeric structure of solid C₅H₅FeC₅H₄COOSn(CHCH₂)₃ has been established by X-ray crystallography. The crystals are monoclinic, space group P2₁/a, with a 15.105(5), b 10.030(4), c 11.402(4) Å, and β 104.06(4)°. In this compound the tin atoms are five-coordinate trigonal bipiramidal, with the vinyl groups equatorial and two apical oxygen atoms from bridging carboxylato groups. The resulting structure is a linear polymer with SnO bond lengths of 2.12 and 2.42 Å. The spectra indicate that similar polymeric structure exist also for compounds II and III in the solid state, whereas an equilibrium monomer ? dimer seems to be present in CHCl₃ solution for the compound III.     

Synthesis and crystal structure of azafulgides

Two azafulgides were synthesized and their crystal structures determined by a single crystal X-ray diffraction analysis. The substances crystallized in the following symmetries and cell parameters. C₂₃H₁₉NO₃( 2 ): triclinic space group P&1bar; with a = 7.243(2). b = 10.981(6) and c = 12.672(8)Å, α = 80.40(5)°, β = 75.58(4)° and γ = 77.32(3)° Z = 2; C₁₉H₁₉NO₃( 1 ): orthogonal space group C_2v⁹-Pmc2₁ with a = 8.079(8), b = 12.752(9) and c = 15.752(13)Å, Z=4. The calculated densities are 1.26 and 1.27 g/cm³ respectively for 2 and 1 . The crystal structures were determined by direct methods. The least-squares refinement led to R values of 0.044 and 0.058 for 2 and 1 for 2738 and 952 reflections with I > 3σ-(I) respectively.     

Synthesis,crystal structure,and photoluminescence of a zinc metalloporphyrin

A zinc metalloporphyrin, ZnTCPP(acetone) (1) (TCPP = meso-tetra(4-carboxyphenyl)porphyrin), has been prepared via a solvothermal reaction and structurally characterized by single-crystal X-ray diffraction. Compound 1 features an isolated structure with a planar macrocycle and an embedded zinc ion binded to four pyrrole nitrogen atoms and one acetone oxygen atom. Photoluminescent investigation reveals that compound 1 displays an intensive emission in the red region.     

Synthesis, crystal structure, and transistor performance of tetracene derivatives

The substitution of chloro or bromo groups in tetracene gives rise to the change of crystal structure, having a substantial effect on carrier transport. Halogenated tetracene derivatives were synthesized and grown into single crystals. Monosubstituted 5-bromo- and 5-chlorotetracenes have the herringbone-type structure, while 5,11-dichlorotetracene has the slipped pi stacking structure. Mobility of 5,11-dichlorotetracene was measured to be as high as 1.6 cm2/V.s in single-crystal transistors. The pi stacking structure, which enhances pi orbital overlap and facilitates carrier transport, may thus be responsible for this high mobility.     

Synthesis, crystal structure, and properties of triphenylguanidinium perrhenate hemihydrate

Triphenylguanidinium perrhenate hemihydrate, [(C₆H₅NH)₃C]ReO₄ · 0.5H₂O (I), is synthesized, and its crystal structure and some properties are studied. The colorless extended plate-like crystals of compound I are triclinic (space group $P\bar 1$ , Z = 4, 293 K, a = 9.8716(17), b = 14.093(2), c = 15.439(3)Å, α = 99.632(9)^○, β = 101.802(9)^○, γ = 95.361(10)^○). Compound I has no isostructural analogs, and the conformations of both crystallographically independent triphenylguanidinium cations differ by a higher symmetry (C _3h ) from those for cations of this type in all other structurally studied compounds. The following parameters are determined: the upper limit of the temperature stability of compound I (383 K), the melting point of anhydrous [(C₆H₅NH)₃C]ReO₄ (Ia) of 441 K, the enthalpy of dehydration of compound I (ΔH _dehydr ^{(383 K)} = 10.0(8) kJ/mol), and the enthalpy of melting of anhydrous Ia (ΔH _m ^{(441 K)} = 16.6(9) kJ/mol).     

Combining Fourier transform nuclear quadrupole resonance (FT-NQR) spectroscopy and mass spectrometry (MS) to study the electronic structure of titanocene dichlorides

A combination of nuclear quadrupole resonance spectroscopy (NQR) and mass spectrometry (MS) has been used to observe trends in electronic structure in three titanocenes: bis(cyclopentadienyl) titanium dichloride (η(5)-C(5)H(5))(2)TiCl(2), bis(pentamethylcyclopentadienyl) titanium dichloride (η(5)-C(5)(CH(3))(5))(2)TiCl(2) and dimethylsilylene-bridged ansa bis(cyclopentadienyl) titanium dichloride Si(CH(3))(2)(η(5)-C(5)H(5))(2)TiCl(2). Using MS, electron ionisation mass spectra of these compounds are presented within the context of the entire homologous series with one to five methyl groups on each cyclopentadienyl ligand. A dedicated NQR spectrometer was constructed for this study with a sensitivity sufficient to precisely determine the NQR resonant frequency of (35)Cl atoms using 3 g samples of these titanocenes. The observed frequencies are thus 11.784, 11.930 and 10.863 MHz at 298 K. The results demonstrate that NQR using a relatively simple apparatus can be used as a sensitive and cost effective probe into the molecular structure of organometallic chlorides, which complements the information inferred from the mass spectra.     

Synthesis, crystal structure, and electronic structure of RbVSe2

RbVSe₂ has been synthesized at 773 K through the reaction of V and Se with a Rb₂Se₃ reactive flux. The compound crystallizes in the orthorhombic space group D_2h²⁴-Fddd with 16 formula units in a cell of dimensions , , and at . The structure possesses infinite one-dimensional chains of edge-sharing VSe₄ tetrahedra separated from the Rb⁺ ions. These chains distort slightly to chains. The V-V distance within these chains is 2.8362(4) Å. First-principles total energy calculations indicate that a non-magnetic configuration for the V³⁺ cations is the most stable.     

Electrophilic substitution reaction of indole,part XXIV: Synthesis,characterization, and crystal structure of a novel heterocyclic compound

The reaction of indole with cyclohexanone in the presence of the Lewis acid, boron trifluoride diethyl etherate, resulted in the synthesis of a novel and interesting product ( 1 ) in addition to the bis(indolyl)methane system ( 2 ). The structure of this novel compound has been determined by NMR (¹H and ¹³C) and X‐ray crystal structure analysis. Compound 1 is a (1:2) addition reaction product of indole with cyclohexanone. The spiro six‐membered ring is in the classic chair conformation. An epoxide bridge at C‐4a/C‐10b and the two hydroxyl groups at C‐5a, C‐10a are all on the same side of the central five membered ring. J. Heterocyclic Chem., (2011).     

双乙酰二茂铁缩肼基二硫代甲酸甲酯Schiff碱的合成、晶体结构和生物活性(英文)

用双乙酰二茂铁和肼基二硫代甲酸甲酯为起始原料,制备了含二茂铁的Schiff碱配体[(CH3)SSCNHN=C(CH3)(C5H4)]2Fe.利用元素分析以及红外光谱和单晶X射线衍射分析了产物的组成、化学特征及晶体结构,并测定了其生物活性.结果表明,标题化合物对Ec9706食管癌细胞株具有适度的生长抑制活性.     

1-Phosphinodiazaphosphene: Synthesis,crystal structure,and bonding properties

The iminophosphane, tBu₂P PN NR₂ (RSiMe₃), produced by base-catalyzed elimination of ClSiMe₃ from the corresponding phosphane, possesses an unusually long PN bond (162 pm), which is in accord with quantum chemical calculations.     

Synthesis and crystal structure of maleopimaric acid

The title compound maleopimaric acid was synthesized by a Diels-Alder reaction between maleic anhydride and Pinus elliottii engelm oleoresin at room temperature and it was characterized by single crystal X-ray diffraction. The white crystals crystallized in the orthorhombic system, space group P2(12121) with cell dimensions: a = 7.6960 (15) A, b = 11.851 (2) A, c = 24.577 (5) A, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, V = 2241.6(8) A(3), and R(1) = 0.0716, wR(2) = 0.1975. The two fused and unbridged cyclohexane rings form a trans ring junction with chair conformation with two methyl groups in axis positions, the anhydride ring is planar. Crystal water existed in the molecular and stabilized the structure through intermolecular hydrogen bonds.     

Synthesis and crystal structure of AgInO2

Single crystals of AgInO₂ were obtained by hydrothermal reaction of Ag₂O and In₂O₃ in NaOH at elevated temperature and O₂ pressure. The delafossite type crystal structure was refined using single crystal X-ray diffractometer data (R3m; a_hex = 327.68(7), c_hex = 1887.8(7) pm; Z = 3; R_w = 0.022; 171 independent structure factors). InO and AgO bond distances are 217.4(4) and 207.6(8) pm, respectively. Structure and bond characteristics are discussed.