Metallacrown ethers with a symmetric bis(phosphite) ligand derived from 1,2-bis-(2-hydroxyethoxy)benzene: Synthesis, characterization and hydroformylation of styrene

To better understand the effects of ligand configuration on hydroformylation reactions carried out in the presence of LiBPh₄·3dme (dme = 1,2-dimethoxyethane), a conformationally restrained bis(phosphite) ligand derived from 1,2-bis-(2-hydroxyethoxy)benzene, {[(2,2′-O₂C₁₂H₈)P(C₂H₄O₂)]₂C₆H₄}, 1, has been prepared and its Rh(I) metallacrown ether complex has been evaluated as a catalyst for the hydroformylation of styrene. Both the activity and regioselectivity of the catalyst are sensitive to the amount of the LiBPh₄·3dme added with the activity decreasing by 16% and the regioselectivity for the iso increasing by 9% at a 8:1 LiBPh₄:Rh ratio.Model complexes for the octahedral, cis-Mo(CO)₄(1), 2, and square planar, cis-PtCl₂(1), 3, and cis-PdCl₂(1), 4, complexes in the catalytic cycle has been have been studied using multinuclear NMR spectroscopy and X-ray crystallography. Although the X-ray crystal structure of 2 suggests that the metallacrown ether ring could adopt a configuration capable of binding alkali metal cations, this does not appear to occur in a dichloromethane-d₂ solution of 2 because no shift in the ³¹P NMR resonance 2 is observed upon the addition of an excess of LiBPh₄·3dme. The ³¹P{¹H} NMR spectra of chloroform-d solutions of 2 (in the presence of a catalytic amount of HgCl₂) and of 4 and the X-ray crystal structures of the complexes indicate that the bis(phosphite) ligands are cis coordinated in these complexes in both the solution and in the solid state. This is particularly surprising for 4 because related PdCl₂{Ph₂P(CH₂CH₂O)_nCH₂CH₂PPh₂} (n = 3-5) complexes exhibit both cis-trans and monomer-oligomer equilibria in solution.     

Diode laser noise-spectroscopy of low-frequency atomic fluctuations in rubidium vapor

We have observed resonant features in the spectrum of the fluctuations of a linearly polarized diode laser beam transmitted through a rubidium vapor cell, corresponding to the evolution of the atomic spin in the presence of a constant magnetic field. The observed resonances occur at a noise frequency corresponding to twice the Larmor frequency of ground state rubidium atoms and are due to two-photon Raman processes involving the carrier frequency and the noise sideband. We observed noise resonances for frequencies of the order of one MHz via heterodyne detection. Due to nonlinear Faraday rotation, we detected emitted light with polarization orthogonal to the incident field. The influence of the laser light fluctuations on the transmitted light noise spectrum was investigated by using two diode laser sources with different spectral bandwidths. The observed features are in qualitative agreement with a semiclassical theoretical model that treats laser fluctuations up to first order.     

Preparation and characterization of organotin-oxomolybdate coordination polymers and their use in sulfoxidation catalysis

The organotin-oxomolybdates [(R(3)Sn)(2)MoO(4)].n H(2)O (R=methyl, n-butyl, cyclohexyl, phenyl, benzyl) have been prepared and tested as catalysts for the oxidation of benzothiophene with aqueous hydrogen peroxide, at 35 degrees C and atmospheric pressure. In all cases, the 1,1-dioxide was the only observed product. The kinetic profiles depend on the nature of the tin-bound R group and also on the addition of a co-solvent. For the tribenzyltin derivative, the apparent activation energies for sulfoxidation as a function of the co-solvent are in the order 1,2-dichloroethane (5 kcal mol(-1))相似文献   

Preparation and optical characterization of hydroxyapatite and ceramic systems with titanium and zirconium formed by dry high-energy mechanical alloying

Calcium phosphate-based bioceramics, mainly in the form of hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂—HAP, is the main mineral constituent of teeth and bones with excellent biocompatibility with hard and muscle tissues. These materials exhibit several problems of handling and fabrication, which can be overcome by mixing them with a suitable binder. The dry milling process of fabrication of HAP presents the advantage that melting is not necessary and the powder obtained is nanocrystalline. The high efficiency of the dry milling process opens a new way to produce commercial amount of nanocrystalline HAP and others bioceramic. In this work dry mechanical alloying has been used to produce nanocrystalline powders of HAP using three different experimental procedures (HAPA: Ca(H₂PO₄)₂ + Ca(OH)₂; HAPB: Ca(H₂PO₄)₂ + CaCO₃; and HAPC: CaHPO₄ + CaCO₃). HAP was obtained after 5, 10 and 15 h of milling in the reactions HAPA and HAPB, but it is necessary 15 h of milling in the reaction HAPC to obtain HAP. In order to improve the mechanical properties of HAP calcium phosphate ceramics, with titanium (CaP-Ti) and zirconium (CaP-Zr), have been prepared by dry ball milling using two different experimental procedures: CaP-Ti1: Ca(H₂PO₄)₂ + TiO₂; CaP-Ti2: CaHPO₄ + TiO₂; and CaP-Zr1: Ca(H₂PO₄)₂ + ZrO₂, CaP-Zr2: CaHPO₄ + ZrO₂. The calcium titanium phosphate phase, CaTi₄P₆O₂₄, was obtained in the reaction CaP-Ti1. In the reactions CaP-Ti2, CaP-Zr1 and CaP-Zr2, it was not observed the formation of any calcium phosphate phase even after 15 h of dry mechanical alloying. The milled HAP and the ceramics systems obtained were characterized by X-ray powder diffraction, infrared and Raman scattering spectroscopy.     

Preparation, structure, morphology, and dc and ac conductivity of the 88SiO2-6Li2O-6Nb2O5 (% mole) sol-gel derived glass-ceramics

The glass composition 88SiO₂-6Li₂O-6Nb₂O₅ (mole %) was successfully prepared by the sol-gel technique. The dried and translucent gel was heat-treated at temperatures between 500°C and 800°C. Lithium niobate crystallites, an important ferroelectric material, were detected in the gel derived glass-ceramics treated above 650°C. In the samples treated at 700 and 800°C the Li₂Si₂O₅ crystalline phase is present. The 800°C treated sample also presents the Li₃NbO₄ phase. The structure and morphology of the samples were studied by X-ray powder diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM). The SEM revealed that all the samples, heat-treated above 650°C, present crystallites embedded in the glass matrix. The particles detected in the 600°C treated sample are essentially amorphous, or with an incipient structure. The temperature dependence of the dc electrical conductivity (σ _dc ) shows two regions with different activation energies. The conductivity behaviour of the sample is mainly due to the mobile ion number. The ac conductivity (σ _ac ), measured at 1 kHz decreases with the rise of the treatment temperature due to the increase of the LiNbO₃ crystallites amount. The electrical behavior of the glass and glass-ceramics reflects the important role carried out by the treatment temperature in the gel-glass structure.     

Interpolation of relative retentions as a tool for identification of perhalogenated compounds

Summary Separation of perhalogenated compounds resulting from thermolysis, photolysis or radiolysis of mixtures of halogens in carbon tetrachloride was carried out by programmed temperature gas chromatography. Plots of relative retentions (to CBr₄) vs the number of bromine atoms present for known compounds of the general formula C_xBr_yCl_z (x=1 and 2; y+z=4 or 6) gave three linear correlations (all with r>0.99). These correlations permitted projections of the identities of reaction products for which no standards were available. These projections were later confirmed by CG-MS. *** DIRECT SUPPORT *** A0732166 00010     

Crystal structure of 2,2,4,7,7-pentamethyl-3,6-dithiaoctane tetracarbonyl tungsten(0)

The x-ray crystal structure of the complex ²-PDOW(CO)₄ (five-membered ring, PDO = 2, 2, 4, 7, 7-pentamethyl-3,6-dithiaoctane) is reported. The complex crystallizes in the monoclinic crystal system, space group P2₁/c, [#14] with unit cell parameters a = 14.002(14) Å, b = 9.340(10) Å, c = 15.094(12) Å, = 92.67(4)°, V = 1972(3) ų; Z = 4. The arrangement of the ligands around the metal atom is distorted from octahedral geometry. Large C–O bond distances and short W–C bond distances of the carbonyl groups located at a trans position with respect to PDO is indicative of a trans influence. The W–S(1) and W–S(2) bond distances of 2.545(3) and 2.545(2) Å, respectively, are shorter than observed for closely related complexes.     

Manganese cryptomelane-type oxides: A thermo-kinetic and morphological study

In the present work, a detailed study on structural and textural properties, as well as a thermo-kinetic characterization of two manganese cryptomelane-type oxides, was carried out. A suitable methodology was stated for determining the several stages taking place during the surface molecules’ removal. Thus, further insights were provided about the chemical nature of the sites present at the solid's surface. Relative strengths and the number of basic sites at the surface were estimated. The results show that the removal of the adsorbed (H₂O, CO₂) molecules from the surface is essential to disclose the oxide surface features. The morphological properties and thermo-kinetic characterization indicate the existence of at least three types of basic sites, owing activation energy values ranging from 140 to 190 kJ/mol. The dispersion observed in the activation energy data, during the CO₂ loss, suggests that the interaction occurs on different sites. Therefore, both samples showed a heterogeneous surface; this is related to the energetic nature of the sites, as well as the basic strengths of the surface manganese cryptomelane oxides.     

Amino acid-functionalized cyclopentadienyl molybdenum tricarbonyl complex and its use in catalytic olefin epoxidation

The complex [(N-benzyloxycarbonylprolyl)cyclopentadienyl]-Mo(CO)₃Me was prepared by the reaction of the amino acid-functionalized cyclopentadienyl-lithium reagent with Mo(CO)₆, and subsequent methylation with CH₃I. The complex was characterized by FTIR, ¹H and ¹³C NMR, and elemental analysis. A single-crystal X-ray diffraction study showed that the complex is chiral, crystallizing in the orthorhombic P2₁2₁2₁ space group with the Flack parameter refining to –0.007(16), which unequivocally confirms the presence of an enantiomerically pure compound. The complex was examined as a catalyst precursor in the liquid-phase epoxidation of trans-β-methylstyrene at 280–330 K, using either tert-butylhydroperoxide (tert-BuOOH), cumylhydroperoxide or urea-hydrogen peroxide adduct as oxidant, and, optionally, a co-solvent. With chloroform and tert-BuOOH, the catalytic activity surpasses that previously reported for chiral complexes of the type CpMo(CO)₃X, giving the epoxide isomers ((R,R)-(+) and (S,S)-(?)-1-phenylpropylene oxide) in excellent selectivity, albeit with negligible enantiomeric excess. FTIR spectroscopy showed that the oxidative decarbonylation of the tricarbonyl complex with tert-BuOOH is fast under the reaction conditions used, and that the structural integrity of the amino acid-functionalized cyclopentadienyl group is retained during this process. The use of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate as a solvent for the catalyst generates a biphasic liquid–liquid reaction system that enables, at the end of a catalytic cycle, the separation and reutilization of the catalyst.