Search results for "Reactivity"
showing 10 items of 880 documents
Synthesis of Dirhodium(II) Complexes with Several Cyclometalated Thienylphosphines
2006
The thermal reaction of dirhodium tetraacetate with tris(3-thienyl)phosphine (3TP), diphenyl(3-thienyl)phosphine (3TPPh2), and diphenyl(2-thienyl)phosphine (2TPPh2) gives rise to mono-cyclometalated and bis-cyclometalated compounds; the latter can have a head-to-head (H−H) or head-to-tail (H−T) configuration. Bis-cyclometalated compounds with H−T configuration can be prepared in high yield under photochemical conditions or by combining irradiation with subsequent thermal treatment in acetic acid. The reactivity order of aromatic ring C−H activation is phenyl < 2-thienyl ≪ 3-thienyl, which leads to a selective activation of the thienyl ring. Thus, only one mono-cyclometalated compound is obt…
Reactivity of the Superheavy Element 115, Mc, and Its Lighter Homologue, Bi, with Respect to Gold and Hydroxylated Quartz Surfaces from Periodic Rela…
2021
Adsorption energies (Eads) of the superheavy element (SHE) Mc, its lighter homologue (Bi), as well as of another superheavy element Nh and some lighter homologues of SHEs on gold and hydroxylated quartz surfaces are predicted via periodic relativistic density functional theory calculations. The aim of this study is to support "one-atom-at-a-time" gas-phase chromatography experiments that are examining the reactivity and volatility of Mc. The obtained Eads values of the Bi and Mc atoms on the Au(111) surface are >200 kJ/mol. On the hydroxylated quartz surface, Mc should adsorb with a minimal energy of 58 kJ/mol. On both types of surfaces, Eads(Mc) should be ∼100 kJ/mol smaller than Eads(Bi) …
1H-naphtho[2,1-b]thiete and 2H-naphtho[2,3-b]thiete- synthesis and reactivity
1994
Abstract The title compounds 4 and 8 are obtained by flash vacuum pyrolysis of the corresponding hydroxymethylthionaphthols 3 and 7. Whereas 4 shows a smooth ring opening on heating, 8 is thermally stable but reacts photochemically. The different behavior is explained on the basis of an MNDO calculation. The valence isomers 4′ and 8′ represent thioquinonemethides, which are highly reactive components in [12π + 2π]cycloaddition processes (4 → 9, 10, 11; 8 → 12).
ChemInform Abstract: 1H-Naphtho(2,1-b)thiete and 2H-Naphtho(2,3-b)thiete - Synthesis and Reactivity.
2010
Abstract The title compounds 4 and 8 are obtained by flash vacuum pyrolysis of the corresponding hydroxymethylthionaphthols 3 and 7. Whereas 4 shows a smooth ring opening on heating, 8 is thermally stable but reacts photochemically. The different behavior is explained on the basis of an MNDO calculation. The valence isomers 4′ and 8′ represent thioquinonemethides, which are highly reactive components in [12π + 2π]cycloaddition processes (4 → 9, 10, 11; 8 → 12).
Moral values, empathy and identification with fictional characters: the representative universe at “Cuéntame cómo pasó” (TVE)
2012
En la presente investigación se muestran los resultados de un estudio de base experimental sobre el análisis de los valores morales presentes en la serie emitida por Televisión Española “Cuéntame cómo pasó”. La discusión se centra en los valores morales como el aspecto nuclear de este constructo audiovisual, en especial en su posible correlación con la identificación de los personajes y la empatía ficcional del formato. En el estudio participaron 47 estudiantes universitarios y 36 personas de más edad, quienes fueron sometidos a unos cuestionarios analíticos anteriores y posteriores al visionado de dos capítulos de la serie televisiva. Tras la aplicación pre-test y post-test de la Escala de…
Synthesis, structural studies and reactivity of vanadium complexes with tridentate (OSO) ligand
2007
The direct reaction between [VCl(3)(thf)3] or [VO(OEt)3] and 2,2'-thiobis{4-(1,1,3,3-tetramethyl-butyl)phenol (tbopH(2)) leads to the formation of [V(2)(micro-tbop-kappa(3)O,S,O)2Cl(2)(CH(3)CN)(2)] (1).4CH(3)CN or [V(2)(micro-OEt)2(O)2(tbop-kappa(3)O,S,O)2] (2), respectively, in high yield. Compounds 1 and 2 were characterized by chemical and physical techniques including X-ray crystallography and variable temperature magnetic susceptibility studies (J = -29.1 cm(-1)) for 1. Complexes 1 and 2 were supported on MgCl2 and when activated with aluminium alkyls, were found to effectively polymerize ethene to produce polyethylene with a narrow molecular weight distribution M(w)/M(n) approximately…
Variations of vitamin D-like reactivity in the crustacean Orchestia cavimana during the molt cycle
1991
An investigation into vitamin D-like molecules has been performed on whole extracts of the terrestrial amphipod Orchestia cavimana, using a sensitive nonequilibrium assay employing 1,25-(OH)2 D receptor from calf thymus. Relatively large amounts of these secosteroid-like molecules were observed and they varied in concentration according to the stages of the molt cycle. The amplitude of these variations reaches a ratio of about 40 from the minimum in premolt to the intermolt sharp peak.
New insights in chemical reactivity from quantum chemical topology.
2021
International audience; Based on the quantum chemical topology of the modified electron localization function ELFx, an efficient and robust mechanistic methodology designed to identify the favorable reaction pathway between two reactants is proposed. We first recall and reshape how the supermolecular interaction energy can be evaluated from only three distinct terms, namely the intermolecular coulomb energy, the intermolecular exchange‐correlation energy and the intramolecular energies of reactants. Thereafter, we show that the reactivity between the reactants is driven by the first‐order variation in the coulomb intermolecular energy defined in terms of the response to changes in the numbe…
Direct NMR evidence for the dissociation of sulfur-dioxide-bound acetaldehyde under acidic conditions: Impact on wines oxidative stability
2021
Abstract SO2 reaction with electrophilic species present in wine, including in particular carbonyl compounds, is responsible for the reduction of its protective effect during wine aging. In the present study, direct 1H NMR profiling used to monitor the reactivity of SO2 with acetaldehyde under wine-like oxidation conditions. The dissociation of acetaldehyde bound SO2 was evidenced suggesting that released free SO2 can further act as an antioxidant. EPR and DPPH assays showed an increasing antioxidant capacity of wine with the increase in the concentration of acetaldehyde sulfonate. The presence of acetaldehyde sulfonate in wines was correlated with the overall antioxidant activity of wines.…
Competitive and Selective Csp3Br versus Csp2Br Bond Activation in Palladium-Catalysed Suzuki Cross-Coupling: An Experimental and Theoretical Study …
2010
Phosphine ligands have been demonstrated to have an effect on reactivity and selectivity in the competitive intramolecular palladium-catalysed Suzuki-Miyaura coupling of dibromo sulfoxide 1a possessing two different hybridised electrophilic carbons. It was found that the bromine bond to the sp(3)-hybridised carbon is selectively replaced in the presence of unhindered phosphines such as PPh(3) or xantphos. The use of hindered phosphine ligands such as P(o-tol)(3) and P(1-naphthyl)(3) reversed the selectivity, conducting the cross-coupling at the Csp(2)-Br. Identical trends were observed in external competition experiments carried out with bromomethyl sulfoxide and different substituted bromo…