Effects of inorganic components on the structure and thermo-oxidative degradation of PMMA modified metal alkoxide–EAA complex

Poly(methyl methacrylate) (PMMA) modified titanium and zirconium n-butoxide–ethyl acetoacetate (EAA) complex [M5-Ti(OBuⁿ)₂(EAA)₂ and M5-Zr(OBuⁿ)₂(EAA)₂] were obtained from trialkoxysilane-functional PMMA and EAA modified titanium and zirconium alkoxide via the sol–gel method. Infrared (IR), ¹³C nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis (TGA) were used to analyze the structures and properties of the hybrids with various proportions of metal oxide species. The effect of the complex of metal oxides and EAA ligands on structure and thermo-oxidative degradation of the M5-Ti(OBuⁿ)₂(EAA)₂ and M5-Zr(OBuⁿ)₂(EAA)₂ hybrids were investigated in this study. The ¹H spin–diffusion path length of the hybrids was in a nanometer scale as estimated from the spin–lattice relaxation time in a rotating frame (T_1ρ^H). The apparent activation energies (E_a), evaluated by van Krevelen’s method, for random scission of PMMA segments in hybrids decreased with increasing metal oxide content.     

Microstructures of Alkoxide-Derived Barium Osumilite (BaMg2Al6Si9O30) Glass Ceramics

The crystallisation sequence of stoichiometric barium osumilite prepared by partial-alkoxide (PAR) and all-alkoxide routes (AAR) and the microstructure of the fully crystallised glass ceramic were examined. Comparing the crystallisation behaviours of the gel-glasses obtained revealed that the first phase to crystallise was mullite in PAR but hexacelsian in AAR. Barium osumilite crystals grew randomly and more homogeneously in PAR while in AAR larger barium osumilite crystals grew in clusters. Cordierite formed as a secondary phase in both routes and it crystallised on and between the osumilite lamellae. Mullite and hexacelsian also persisted up to the stage when full crystallisation and taken place.     

Synthesis of Hafnia Powders and Nanofiltration Membranes by Sol-Gel Process

Hafnia nanofiltration membranes were prepared by sol-gel process from hafnium 1-methoxy-2 propoxide via colloidal route. This original molecular precursor has been synthesized and characterized by ¹H NMR, mass spectroscopy, infrared and elemental analysis. Its peptization revealed to be the most efficient method to provide a highly reactive powder at a low sintering temperature. The porous volume variation and the pore diameter distribution of the hafnia powder have been studied as a function of the sintering temperature and the TGA, DTA and dilatometry study are reported. The membrane sintered at 450°C exhibited a defect-free texture with a cut-off equals to 420 Daltons and pore diameters equal to 1.9 nanometers.     

Hydrolysis-condensation reactions of titanium alkoxides in thin films: A study of the steric hindrance effect by X-ray photoelectron spectroscopy

An original approach based on X-ray photoelectron spectroscopy (XPS) is proposed to study the influence of the surrounding humidity on the hydrolysis-condensation reactions of five titanium alkoxides in thin films. More precisely, the influence of the nature of the ligands (propoxide, butoxide, isopropoxide, phenoxide, and 9H-carbazole-9-yl-ethyl-oxy) on the reaction rate was evidenced. The reaction advancement was evaluated by comparing XPS chemical compositions to theoretical compositions calculated for all the possible rates. XPS chemical environment information allowed validating the reliability of this approach through the evaluation of the condensation state. In both approaches, the influence of the steric hindrance on the reactivity of titanium alkoxides was highlighted to be similar to what has been previously observed in solution. Theses results corroborate the validity of our XPS approach to determine titanium alkoxide hydrolysis-condensation reactions in the specific application of thin films.     

Synthesis,spectroscopic and X‐ray single‐crystal structure study of bis(2‐methoxy‐ethanolato)‐bis(8‐quinolinato)titanium(IV)

Reaction of Ti(OCH₂CH₂OR)₄ (R?CH₃ and C₂H₅) with 8‐hydroxyquinoline in benzene at room temperature resulted in the formation of Ti(C₉H₆NO)₂(OCH₂CH₂OR)₂, characterized by IR, ¹H‐NMR, UV and mass spectroscopies. The molecular structure of Ti(C₉H₆NO)₂(OCH₂CH₂OCH₃)₂ has been determined by single‐crystal X‐ray structure analysis. The geometry at titanium is a distorted octahedron, with the nitrogen atoms of quinolinate occupying the trans position with respect to oxygens of the 2‐methoxyethoxy groups. The prepared quinolinate derivatives of titanium alkoxides are very stable towards hydrolysis and harsh conditions are required for hydrolytic cleavage. Copyright © 2005 John Wiley & Sons, Ltd.     

Cerium Alkoxides—Synthesis, Properties and Their Use in Michael Addition Reaction

Cerium(III) alkoxides served as an effective and attractive promoter for the Michael addition reaction with excellent chemical yields under mild conditions in short reaction time.     

Unusual structurally characterized pyridine carbinoxide copper(II) coordination compounds,isolated from organic solvents

The coordination behavior of pyridine carbinoxide [NC₅H₄(CH₂O)-2 or OPy] with copper in organic solvents was crystallographically determined. Initial attempts to generate the Cu(II) OPy derivatives from an alcoholysis exchange of Cu(OCH₃)₂, with H–OPy in toluene, led to the isolation of [Cu(µ_c-OPy)(O^cPy)]₂ (1, “c” indicates chelation). The square-based pyramidal geometries noted for each Cu center resulted from one O^cPy and two µ_c-OPy ligands, generating an unusual C_i symmetry. From the reaction of H–OPy and the Cu(I) species Cu(C₆H₂(CH₃)₃-2,4,6), mononuclear Cu(II) complex Cu(O^cPy)₂(H–OPy)₂ (2) was isolated. Compound 2 is unusual in that it adopts a square planar arrangement around the Cu metal center using two O^cPy ligands; however, the metal center also coordinates with two H–OPy molecules forming an octahedral geometry. Upon dissolution in water, both 1 and 2 react to form the previously reported Cu(O^cPy)₂ · 2H₂O (3). Attempts to add a Lewis base through dissolution of 1 in selected solvents (i.e., tetrahydrofuran, pyridine, 1-methylimidazole) led to [Cu(µ_c-OPy)(O^cPy)]₂ · H₂O (4), which possesses a C ₂ symmetry. The water was believed to be extracted from the “dry” solvents. A Cl derivative was also solved for the Cu(II)/Cu(I) species [Cu(OPy)₂]₂[CuCl(H–OPy)₂]₂ (5) from tetrahydrofuran dried over apparently contaminated sieves.     

Aluminum 2-Methoxyethoxide: An Internally Coordinated Aluminum Alkoxede

Abstract

Aluminum 2-methoxyethoxide was isolated and characterized by ¹H, ¹³C and ²⁷Al NMR. The ²⁷Al NMR and mass spectra show that the compound is an internally coordinated dimer. This aluminum alkoxide is less susceptible to hydrolysis in comparison to other aluminum alkoxides.     

Synthesis,Characterization and Photocatalytic Activity of TiO<Subscript>2</Subscript> Powders Prepared Under Different Gelling and Pressure Conditions

Homogeneous TiO₂ gel powders were prepared by hydrolysis and condensation of titanium(IV) isopropoxide with HCl or SnCl₂ catalysts, by working under reduced pressure or in air. Ti(IV) alkoxide was previously modified by reaction with formic or acetic acid, used as chelating ligands, when gelation was performed in acidic catalysis. Crude TiO₂ xerogels were purified by water reflux treatment in order to induce a low temperature crystallisation to the anatase phase. Both crude and purified TiO₂ samples were characterised by XRD, FT-IR, SEM, and N₂ adsorption analysis. Thermoanalyses (TG, DTA, DTG, TG-MS, TG-GC-MS) were carried out to quantify the residual organic components in the crude TiO₂ gels and to obtain stoichiometric formulas to describe their chemical compositions. XRD data of purified TiO₂ powders were processed by means of a Rietveld refinement procedure to determine TiO₂ polymorphs, crystallite sizes and cell parameters, before their use in photocatalytic tests. The photoactivity of the purified TiO₂ anatase powders was studied by using 4-nitrophenol degradation as probe reaction carried out in a batch and/or a membrane photoreactor. Samples prepared by using formic acid or SnCl₂ were the most photoactive, whereas specimens gelled under vacuum treatment showed detrimental effects.     

Interconverting WW Triple Bonds and W4 Clusters: Structures of W4(OPrn)16 and [Li2W2(OPrn)8(DME)]2*

Alcoholysis of W₂(NMe₂)₆ with excess n-propanol in hexane yields the tetranuclear cluster, W₄(OPrⁿ, I. Reduction of I with two equivalents of Li₂COT in THF gives a small yield of Li₂W₂(OPrⁿ)₈. Single crystals were isolated by cooling the product mixture in DME and were shown to be [Li₂W₂(OPrⁿ)₈(DME)]₂, II, which consists of a unique “dimer of dimers” structure. In this reaction sequence, W₄¹⁶⁺ cluster formation is followed by four electron reduction to reform the (W≡W)⁶⁺ unit. Better yields of the lithium salt can be obtained by the addition of LiOPrⁿ/HOPrⁿ solutions to W₂(OBu^t)₆ in which case Li₂W₂(OPrⁿ)₈ has been obtained as a 1:1 adduct with LiOPr. This identity of this salt was confirmed by solution NMR spectroscopy. In the alternative reaction, the (W≡W)⁶⁺ center remains intact from reactant to product. No attempt has been made to separate the product from excess LiOPr. DFT (ADF 2004.01) molecular orbital calculations on the model cluster W₄(OH)₁₆ are used to help elucidate the disruption of the W₄ cluster upon four electron reduction. The molecular structures of compounds I and II are reported.*Dedicated to Professor F. A Cotton on the occasion of his 75th birthday.