Search results for "element"

Observation of chemical reactions between alkaline-earth oxides and tungsten at high pressure and high temperature

2009

Abstract The potential chemical reactions of alkaline-earth oxides (AeO with Ae: Mg, Ca, Sr, and Ba) and tungsten are studied at high pressure and high temperature. At pressures ranging from 5 to 10 GPa and temperatures of 2000 K, a noticeable reaction between AeO and powder tungsten (W) was detected. As a product of the reaction, scheelite-structured orthotungstates (AeWO 4 ) were formed. The reactivity of alkaline-earth oxides with tungsten increases in the order Ca 2 →AeWO 4 .

Insights into the decomposition pathway of a lutetium alkylamido complex via intramolecular C–H bond activation

2017

Abstract Synthesis, characterization and reaction chemistry of lutetium alkylamido LLu(CH2SiMe3)(NHCPh3) (2), L = 2,5-[Ph2P=N(4-iPrC6H4)]2N(C4H2)–, is reported. Complex 2 undergoes cyclometalation of the NHCPh3 ligand at elevated temperatures to produce the orthometalated complex LLu(κ2−N,C-(NHCPh2(C6H4))) (3) which converts to 0.5 equivalents of bis(amido) LLu(NHCPh3)2 (4) upon heating at 80 °C for 24 h. Reaction of complex 2 with 4-dimethylaminopyridine (DMAP) does not promote alkane elimination nor imido formation. A kinetic analysis of the thermal decomposition of complex 2, supported by deuterium labelling studies and computational analysis (PBE0/def2-TZVP/SDD(Lu)), indicate direct Csp…

Measuring the Relative Reactivity of the Carbon-Hydrogen Bonds of Alkanes as Nucleophiles

2018

We report quantitative measurements of the relative reactivities of a series of C-H bonds of gaseous or liquid CnH2n+2 alkanes (n = 1-8, 29 different C-H bonds) towards insitu generated electrophiles (copper, silver, and rhodium carbenes), with methane as the reference. This strategy surpasses the drawback of previous model reactions of alkanes with strong electrophiles suffering from C-C cleavage processes, which precluded direct comparison of the relative reactivities of alkane C-H bonds.

2001

A new manganese(III) oxamato dimer possesing an unprecedented Mn2(μ-O2CR)(μ-OH2⋯O2 CR) core has been synthesised, structurally and magnetically characterised, and used as a catalyst for the oxidation of alkanes to alcohols and ketones by ButO2H and O2 in CH2Cl2 at rt.

On the influence of the acid-base character of catalysts on the oxidative dehydrogenation of alkanes

1996

Vanadium oxides supported on metal oxide, i.e. Al2O3, MgO and Mg-Al mixed oxide, and V-containing microporous materials (VAPO-5 and MgVAPO-5) have been tested in the oxidative dehydrogenation of C2-C4 alkanes. In all cases, tetrahedral vanadium species (isolated and/or associated) were mainly observed from51V-NMR and diffuse reflectance spectroscopies. The reducibility of V5+-species, determined from the onset-reduction temperature, decreases as follows: VOx/AL > VAPO-5 > MgVAPO-5 =VOx/MG > VOx/MG + AL. The acid character of catalysts, determined from the FTIR spectra of pyridine adsorbed, decreases as: MgVAPO-5 > VOx/AL > VAPO-5 > VOx/MG + AL > VOx/MG. A similar trend between V-reducibilit…

Deep oxidation of volatile organic compounds using ordered cobalt oxides prepared by a nanocasting route

2010

Ordered Co3O4 with high surface area (until 173 m2/g) has been successfully obtained through a nanocasting route using mesoporous KIT-6 silica as a hard template and tested in the deep oxidation of a series of representative volatile organic compounds (VOCs): propane as a model of short chain alkane and toluene as a model of monoaromatic hydrocarbon. It has been demonstrated that the catalytic activity for VOC deep oxidation is very elevated and its catalytic stability at moderate temperatures very good. However, the role of the ordered structure in the catalytic performance does not seem to be beneficial. The enhanced catalytic activity has been explained in terms of both the high surface …

Theoretical characterization of iron and manganese porphyrins for catalyzed saturated alkane hydroxylations

1997

Abstract The theoretical characterization of porphin (H2Por), iron and manganese porphyrins MIII(Por) and their chlorine derivatives MIII(Por)Cl has been carried out. This work represents a first step for modelling catalyzed saturated alkane hydroxylations. The chlorine atom is responsible for the existence of a dipole moment of 1.2–2.0 D in the MIII(Por)Cl molecules and for a negative value of the mean quadrupole moment (−16–(−14)DA). The charge of the metal atom (1.8–2.2 e) is rather varied (to 2.1–2.6 e) and the effective polarizability (2.8–2.9 A3) is increased (to 3.5–3.6 A3) by the addition of the chlorine atom. Starting from the porphin molecule, the presence of the metal atom decrea…

Functionalization of CnH2n+2Alkanes: Supercritical Carbon Dioxide Enhances the Reactivity towards Primary Carbon-Hydrogen Bonds

2015

The functionalization of the primary sites of alkanes is one of the more challenging areas in catalysis. In this context, a novel effect has been discovered that is responsible for an enhancement in the reactivity of the primary C-H bonds of alkanes in a catalytic system. The copper complex Cu(NCMe) (=hydrotris{[3,5-bis(trifluoromethyl)-4-bromo]-pyrazol-1-yl}borate) catalyzes the functionalization of CnH2n+2 with ethyl diazoacetate upon inserting the CHCO2Et unit into C-H bonds. In addition, the selectivity of the reaction toward the primary sites significantly increased relative to that obtained in neat alkane upon using supercritical carbon dioxide as the reaction medium. This was attribu…

Bis(3,5-dimethylpyrazol-1-ato) zirconium complexes as precursors for ethylene polymerisation upon activation with MAO: Syntheses, characterisation an…

2007

Abstract The bis(3,5-dimethylpyrazol-1-ato) zirconium complex [Zr(η2-3,5-Me2Pz)2(NMe2)2(NHMe2)2] (2) is obtained by treatment of [Zr(NMe2)4] with 2 equiv. of 3,5-dimethylpyrazole 1. The reaction of the [ZrCl4(THF)2] adduct with 2 equiv. of the potassium salt of 1 affords the dichloro derivative [Zr(η2-3,5-Me2Pz)2Cl2]n (3), while reaction with 4.1 equiv. of 1 in the presence of 2.1 equiv. of NEt3 affords the dichloro pyrazole adduct [Zr(η2-3,5-Me2Pz)2Cl2(η1-3,5-Me2PzH)2] (4). Treatment of [Zr(CH2Ph)4] with 2 equiv. of 1 gives the dibenzyl complex [Zr(η2-3,5-Me2Pz)2(CH2Ph)2] (5) via alkane elimination. Compound 4 presents fluxional behaviour in CDCl3 solution, which was studied and quantified…

Supramolecular Aggregates in Vacuum: Positively Mono-Charged Sodium Alkanesulfonate Clusters

2010

The formation and structural features of positively mono-charged aggregates of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and sodium methane—(MetS), butane—(ButS) and octane—(OctS) sulfonate molecules in the gas phase have been investigated by electrospray ionization mass spectrometry, energy-resolved mass spectrometry and density functional theory (DFT) calculations. The experimental results show that the center-of-mass collision energy required to dissociate 50% of these mono-charged aggregates scantly depends on the length of the alkyl chain as well as on the aggregation number. This, together with the large predominance of mono-charged species in the mass spectra, was rationalized i…