Search results for "Density"

Lithium Cation-Catalyzed Benzene Diels-Alder Reaction: Insights on the Molecular Mechanism Within the Molecular Electron Density Theory.

2020

The lithium cation Li+-catalyzed Diels-Alder (DA) reactions of benzene toward a series of acetylenes of improved nucleophilicity can be described within the context of the molecular electron density theory (MEDT) at the ωB97XD/6-311G(d,p) level. Conceptual density functional theory indices characterize the crown ether solvated complex benzene-lithium Bz-Li-Cro as a superelectrophile. Coordination of a lithium cation to benzene does not change substantially the electron localization function electronic structure of benzene. The DA reaction of Bz-Li-Cro with acetylene shows a reduction of the energy of activation of 6.9 kcal·mol-1, which is not sufficient for the reaction to take place, thus …

Theoretical Studies of the Reactivity of Cyclopentadienyl Nitrosyl Alkyl Species of Molybdenum and Tungsten

2000

International audience; The reactivity differences observed experimentally for Cp*W(NO)(CH2CMe3)2 and CpMo(NO)(CH2CMe3)2 have been investigated using density functional theory (DFT) techniques. The reactions of the CpW(NO)(CH2) model complex with NH3 and CH4 are more exothermic and have lower activation barriers than the corresponding processes for CpMo(NO)(CH2). The η2(C,H) methane complex CpM(NO)(CH2)(CH4) (M = Mo, W) can undergo two competitive processes:  C−H activation to afford CpM(NO)(CH3)2 or loss of methane. The relative barrier heights are almost identical for M = W, whereas the formation of CpM(NO)(CH3)2 is significantly disfavored for M = Mo. The activation of C−H and N−H bonds …

Tri- and tetranuclear heteropivalate complexes with core {Fe2Ni O} (x = 1, 2): Synthesis, structure, magnetic and thermal properties

2019

Abstract The reactions of complex [Fe2Ni(O)(Piv)6(Et2O)(H2O)2] (1) with 1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy) gave the following new coordination compounds: the trinuclear complex [Fe2Ni(O)(Piv)6(phen)H2O]·(C2H5)2O (2), the tetranuclear ones [Fe2Ni2(OH)2(Piv)8(phen)2] (3) and [Fe2Ni2(OH)2(Piv)8(bpy)2] (4), depending on the crystallization conditions. According to single crystal X-ray diffraction data, all the compounds have molecular structures. The Mossbauer spectra of 1–3 correspond to high-spin Fe3+ ions in an octahedral environment consisting of oxygen atoms. The DC magnetic susceptibility studies and quantum-chemical analysis of intra- and intermolecular J pathways using…

Peroxydation in vivo et in vitro des acides gras polyinsaturés

2007

It is well admitted that polyunsaturated fatty acids are the most sensitive fatty acids to oxidative damage because of their high number of double bonds. This concept could not be confirmed by in vitro, animal, or human studies since unexpected or even contradictory results were obtained. The explanation of that is probably related to the methods evaluating lipid peroxidation whose relevance is not always established, but especially to movements of polyunsaturated fatty acids within lipoproteins that results in their protection. This short review aims to discuss the main results related to this topic.

1992

The molecular packing and spatial correlations of polymers [CH 2 CR(COOR')] n (R= H, Me; R'= (CH 2 ) 11 + NMe 2 (CH 2 ) 3 SO 3 - ; (CH 2 ) 2 + N(Me)[(CH 2 ) 3 SO 3 - ][C 10 H 21 ]) are studied by means of X-ray analysis and conformational calculations. The analysis of the correlation functions and density distribution profiles suggest a double-layered molecular packing which is discussed for the three polymers investigated, with respect to their different chemical structures. Whereas the zwitterionic polymethacrylates studied exhibit liquid-like short-range order, the polyacrylate analog exhibits an ordered double-layered superstructure

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…

Aziridination of Aromatic Aldimines Through Stabilized Ammonium Ylides: A Molecular Electron Density Theory Study

2019

2,4,5-Trimethylimidazolium Scaffold for Anion Recognition Receptors Acting Through Charge-Assisted Aliphatic and Aromatic C–H Interactions

2016

A series of two-armed 2,4,5-trimethylimidazolium-based oxoanion receptors, which incorporate two end-capped photoactive anthracene rings, being the central core an aromatic or heteroaromatic ring, has been designed. In the presence of HP2O7(3-), H2PO4(-), and SO4(2-) anions, (1)H- and (31)P NMR spectroscopical data clearly indicate the simultaneous occurrence of several charge-assisted aliphatic and aromatic C-H noncovalent interactions, i.e., significant downfield shifts were observed for the imidazolium C(2)-CH3 protons, the methylene N-CH2 protons, and the inner aromatic proton or the outer heteroaromatic protons. Density functional theory calculations confirm the occurrence of these non…

The antioxidant effect in controlling thermal degradation of a low density polyethylene blown film

2004

Abstract It is well known that antioxidants are widely used to prevent thermal degradation of high density and linear low density polyethylene. Antioxidants are not always present in low density polyethylene and only small amounts are usually added to these resins. In this work the effect of an antioxidant system on a low density resin having MFI (190 °C/2.16 kg)=2 g/10′ and density 0.9230 g/cm3 has been studied. Its effect on melt viscosity has been studied by means of a batch mixer and the torque vs time behaviour has been analysed. The results show that a maximum in the torque vs time curve can be seen for the material containing antioxidant. In contrast, the material without antioxidant…

Ionic polymers based on dextran: hydrodynamic properties in aqueous solution and solvent mixtures.

2009

Hydrodynamic properties of a series of ionic polysaccharides with different charge density but the same molecular weight have been evaluated in salt-free aqueous solution and aqueous/organic solvent mixtures by means of capillary viscometry. The polyelectrolytes investigated contain quaternary ammonium salt groups, N-ethyl-N,N-dimethyl-2-hydroxypropylammonium chloride, attached to a dextran backbone. The experimental viscometric data have been plotted in terms of the Wolf method. The results show that the experimental data fit well with this model and allow the calculation of intrinsic viscosities and other hydrodynamic parameters, which provide new information about the dependence of the p…