Search results for "Metallocene"
showing 10 items of 109 documents
Magnesium chloride modified with organoaluminium compounds as a support of the zirconocene catalyst for ethylene polymerisation
2004
Abstract This work describes the influence of the modification of the MgCl2(THF)2 and MgCl2 magnesium supports with the AlEt2Cl, MAO, AlEt3, AlMe3, and AlEt2Cl alkylaluminium compounds on heterogenisation of the bis(cyclopentadienyl) zirconium(IV) dichloride Cp2ZrCl2 catalyst. It was found that only the MgCl2(THF)2 support modified with AlEt2Cl gave the heterogeneous catalyst. On the contrary, application of a magnesium carrier modified by AlEt3, AlMe3, and MAO compounds only results in a homogeneous zirconocene catalyst.
Heterogeneous zirconocene catalyst on magnesium support MgCl2(THF)2 modified by AlEt2Cl for ethylene polymerisation
2005
Abstract The heterogeneous bis(cyclopentadienyl)zirconium(IV) dichloride catalyst of the composition MgCl2(THF)/(AlEt2Cl)0.34/(Cp2ZrCl2)0.01 as determined by FTIR, XRD, and AAS analyses was synthesised and, after activation by MAO, applied for ethylene polymerisation. The catalyst turned out to be stable and more active than those magnesium supported catalysts already known from the literature. The polyethylene produced has a relatively high molecular weight (Mw > 200,000 g/mol), a narrow and monomodal molecular weight distribution (MWD = 2.4), a bulk density of about 180 g/dm3, and monomodal particle size distribution. Application of a ternary Al(i-Bu)3/MAO/B(C6F5)3 activator decreased the…
Novel group 4b ansa-metallocene complexes with the shortest bridge: [1,1′-isopropylydene-3,3′-di-t.Bu-bis(η5-cyclopentadienyl)] Ti and Zr dichlorides
1997
Abstract Reaction of [1,1′-isopropylidene-3,3′-di-tert.butyl-bis(η5-cyclopentadienide)] dilithium with TiCl3, followed by treatment with HCl, and ZrCl4 in various solvent mixtures in the temperature range 0–50°C gives corresponding ansa-metallocene dichlorides as mixtures of the anti/syn-isomers, 1:1. The crystal and molecular structures of three of the four isomers were determined, i.e. rac(anti)-[1,1′-isopropylidene-3,3′-di-tert.butyl-bis(η5-cyclopentadienyl)]TiCl2, space group B2/b, rac(anti)-[1,1′-isopropylidene-3,3′-di-tert.butyl-bis(η5-cyclopentadienyl)]ZrCl2, space group P212121, and meso(syn)-1,1′-[isopropylidene-3,3′-di-tert.butyl-bis(η5-cyclopentadienyl)]ZrCl2, space group P21/n.
Nouveaux complexes cationiques du groupe 4 comme potentielles paires frustrées de Lewis organométalliques : synthèse, réactivité, catalyse
2017
In 2006, the concept of “frustrated Lewis pairs” (called FLPs) was introduced. The main characteristic of these compounds is their ability to activate cooperatively small molecules without the use of a metal (H2, CO2, alkene alkyne…). Initially based on P/B combination, the concept has been extended to several other main group elements (N/B, P/Al, N/Al …). Recently, FLPs have been extended to the transition metal realm. These organometallic FLPs (OmFLPs) are obviously non-metal free systems but they extend significantly the scope of FLP applications. Seeking to develop such systems, a research toward new omFLP combinations (N/Ti+, N/Zr+) has been initiated in our group, based on the synthes…
Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet
2018
Breaking through the nitrogen ceiling Single-molecule magnets could prove useful in miniaturizing a wide variety of devices. However, their application has been severely hindered by the need to cool them to extremely low temperature using liquid helium. Guo et al. now report a dysprosium compound that manifests magnetic hysteresis at temperatures up to 80 kelvin. The principles applied to tuning the ligands in this complex could point the way toward future architectures with even higher temperature performance. Science , this issue p. 1400
Relevance of the Electronegativity of Boron inη5-Coordinating Ligands: Regioselective Monoalkylation and Monoarylation in Cobaltabisdicarbollide[3,3′…
2003
Regioselective monoalkylation and monoarylation in cobaltabisdicarbollide clusters has been achieved starting from Cs[8-I-3,3'-Co(1,2-C 2 B 9 H 1 0 )(1',2'-C 2 B 9 H 1 1 )] by cross-coupling reactions between a B-I fragment andan appropriate Grignard reagent in the presence of a Pd catalyst and CuT. A considerable number of monoalkylated and monoarylated derivatives have been synthesized, which allowed study of the influence of boron in metallocene-type ligands and the effect of alkyl and aryl substituents on boron in boron anionic clusters. Experimental data from UV/ Vis spectroscopy, E 1 / 2 measurements, and X-ray diffraction analysis, and supported by EHMO and ab initio analyses, indica…
C2-Symmetric Ferrocene-Bis(ureido)peptides : Synthesis, Conformation and Solid-State Structure
2009
The extension of peptide derivatives of ferrocene-1,1'-dicarboxylic acid by formal insertion of NH units between ferrocene and peptide strands results in ferrocene-bis(ureido)-peptides. Experimentally, alanine and dialanine methyl esters were attached to the 1- and 1'-position of 1,1'-diiso-cyanoferrocene to give the corresponding bis(ureido)peptide derivatives 3 and 4. The conformation of 3 has been determined in the solid state by X-ray crystallography. In solution the preferred conformation of 3 and 4 has been elucidated by NMR, IR and CD spectroscopy in concert with DFT calculations. The secondary structure of ferrocene―bis(ureido)peptides 3 and 4 is determined by double bifurcated intr…
Biphasic ethylene polymerisation using ionic liquid over a titanocene catalyst activated by an alkyl aluminium compound
2007
Abstract 1-n-Butyl-3-methylimidazolium tetrachloroaluminate ([BMIM]+[AlCl4]−) was applied to biphasic ionic liquid/hexane ethylene polymerisation as a medium of the Cp2TiCl2 titanocene catalyst activated by alkylaluminium compounds (MAO, AlEt2Cl, AlEt3). The best results were obtained using AlEt2Cl. The results show that catalyst recycling, higher ethylene pressure, and greater Al/Ti molar ratio along with a greater volume of the ionic liquid phase enhance catalyst activity. The polyethylene gathered from the hexane phase is characterised primarily by its high purity. Its physical properties remain polyethylene obtained over a heterogeneous metallocene catalyst. Thus, biphasic ionic liquid …
The use of metallocenic esters of n-hydroxysuccinimide for metallohapten synthesis
1991
Different organometallic markers have been described in a new technique for the labelling of many drugs. Thus metallocenic esters of [M = (;CO)3CrC6H5; (;CO)3CrC6H5(;CH2)3; η-C5H5FeC5H4; (;CO)3MnηC5H4; (;CO)3MnηC5H4COCH2CH2; ηC5H4(;ηC5H5)Co+PF−6] react with primary or secondary amine drugs [DRUGNHR] for a psychostimulant drug: amphetamine; tricyclic antidepressants—desipramine and nortriptyline; a vasodilator—histamine; an adrenergic substance—norfenefrine; and for a central stimulant—meth-amphetamine, to give the metallohaptens MCON(;R)—DRUG. All these compounds have been fully characterized by different analytical methods and have potentialities for biological assays. This synthetic route…
Ferrocenyl-Labeled Sugar Amino Acids: Conformation and Properties
2012
Novel organometallic sugar amino acid conjugates 1–5 have been prepared by amide coupling of O-protected N-acetylmuramic acid and iso-muramic acid (2-[3-amino-2, 5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxypropanoic acid) with 1-aminoferrocene, 1-aminoferrocene-1′-carboxylic acid (H-Fca-OH), or 1, 1′-diaminoferrocene, respectively. The influence of the ferrocenyl moiety and presence of additional remote potential hydrogen atom acceptors and donors at the ferrocenyl core on the conformation and lipophilicity is investigated by TLC, IR, NMR, and CD spectroscopic methods augmented by density functional calculations. Furthermore, the redox potential of the ferrocene/ferrocenium couple is tuned by…