Search results for "Reactivity"
showing 10 items of 880 documents
Targeting the Stress System During Gestation: Is Early Handling a Protective Strategy for the Offspring?
2020
The perinatal window is a critical developmental time when abnormal gestational stimuli may alter the development of the stress system that, in turn, influences behavioral and physiological responses in the newborns. Individual differences in stress reactivity are also determined by variations in maternal care, resulting from environmental manipulations. Despite glucocorticoids are the primary programming factor for the offspring's stress response, therapeutic corticosteroids are commonly used during late gestation to prevent preterm negative outcomes, exposing the offspring to potentially aberrant stress reactivity later in life. Thus, in this study, we investigated the consequences of one…
Microstructure of ethylene-1-hexene and ethylene-1-octene copolymers obtained over Ziegler–Natta catalysts supported on MgCl 2 (THF) 2
2001
Abstract The ethylene copolymerizations with 1-hexene or 1-octene in the presence of hydrogen using three catalysts, MgCl 2 (THF) 2 /VOCl 3 /Et 2 AlCl, MgCl 2 (THF) 2 /VCl 4 /Et 2 AlCl, MgCl 2 (THF) 2 /TiCl 4 /Et 2 AlCl, were investigated. It was found that the addition of hydrogen into the copolymerization feed reduces the molecular weight of the copolymers produced and decreases the activity of all the studied catalysts. The microstructure of the copolymers obtained was determined on the basis of 13 C NMR investigations and the reactivity ratios of the comonomers were calculated. The lack of tendency of the olefin comonomers to the creation of the polymer block was confirmed. It was found…
Coordinatively Unsaturated Amidotitanocene Cations with Inverted σ and π Bond Strengths: Controlled Release of Aminyl Radicals and Hydrogenation/Dehy…
2021
Cationic amidotitanocene complexes [Cp2 Ti(NPhAr)][B(C6 F5 )4 ] (Cp=η5 -C5 H5 ; Ar=phenyl (1 a), p-tolyl (1 b), p-anisyl (1 c)) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti-N bond in 1 a-c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a-c undergo photolytic Ti-N cleavage to release Ti(III) species and aminyl radicals ⋅NPhAr. Reaction of 1 b with H3 BNHMe2 results in fast homolytic Ti-N cleavage to give [Cp2 Ti(H3 BNHMe2 )…
On the reactivity of 3-bromo-2-nitrobenzo[ b ]thiophene with nucleophiles: elucidation of the base-catalysed mechanism with rearrangement
2001
Abstract The reactivity of 3-bromo-2-nitrobenzo[b]thiophene (1) with several (anionic and neutral) nucleophiles has been examined. Only with neutral, weak nucleophiles (as anilines) 1 gives, in the presence of non-nucleophilic bases (triethylamine or potassium carbonate), together with the ‘expected’ 3-amino-2-nitrobenzo[b]thiophenes (3) also the ‘unexpected’ 2-amino-3-nitrobenzo[b]thiophenes (4). The composition of the final isomeric mixture depends on the base added (nature and quantity) and on the solvent used. The results demonstrate the relevance of base-catalysis and support a reaction pathway involving the formation of an anionic intermediate (B) which undergoes addition of a second …
[pi]-strain-induced electrophilicity in small cycloalkynes: a dft analysis of the polar cycloaddition of cyclopentyne towards enol ethers
2006
Small cycloalkynes possess a π-strain-induced electrophilicity related to the bending of the C–Csp–Csp bond angle. For cyclopentyne and benzyne, the electrophilicity index defined in the context of density functional theory gives a coherent rationale for the reactivity of these cycloalkynes, which may act as electrophiles in polar cycloaddition reactions toward enol ethers. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Di-n-butyltin oxide as a chemical carbon dioxide capturer
2010
Abstract Several synthetic routes to the decakis(di-n-butyltin(IV)) oxocluster, (n-Bu2SnO)6[(n-Bu2SnOCH3)2(CO3)]2 (1), a diorganotin compound previously shown to belong to the class of organotins able to store carbon dioxide, as well as its reactivity toward dimethyl carbonate (DMC), are described. The synthetic route from n-Bu2SnO and DMC was applied for the preparation of the ethoxy analogue of 1, oxocluster 2, using diethyl carbonate. The structural relationship connecting cluster 1, with its precursor PRE-1 isolated from recycling experiments and n-Bu2SnO is discussed. For this purpose, the reactivity of PRE-1 with trifluoromethanesulfonic acid was investigated in order to trace structu…
Organometallic nucleophiles.A mechanistic study of halide displacement at saturated carbon by 2- and 4-pyridyl complexes of palladium (II) and platin…
1996
Abstract The reactions of the 2- and 4-pyridyl complexes [MX(C 5 H 4 N C n )(dppe)] and trans -[MX(C 5 H 4 N C n )(PPh 3 ) 2 ] (M Pd, Pt; X Cl, Br; n = 2, 4)- involving halide displacement from the organic halides XCH 2 R (X Cl, Br; R CN, Ph, CH CH 2 ) by the pyridyl nitrogen have been studied kinetically by conductivity in acetone or acetonitrile at 25°C. The kinetic data fit the second-order rate law rate k 2 [XCH 2 R][complex], in agreement with an S N 2 process at saturated carbon. The higher rates are displayed by the 2-pyridylplatinum derivatives with X Br in both the metal complex and the organic halide. The higher nucleophilic power of the 2-pyridyl complexes compare…
Orthometallation reactions of rhodium compounds containing orthohaloarylphosphines
1988
The reaction of RhCl3·.3H2O with a 3-molar proportion of P(o-ClC6H4)Ph2, (PCCl) at room temperature gives RhCl(PCCl)2 (1), in high yield. Reaction of [Rh(cot)2Cl]2, (cot = cyclooctene), with PCCl, sol12 molar ratio, also gives compound 1. Refluxing of a solution of 1 in 96% ethanol gives RhCl2(PC)(η2-PCCl), [PC (C6H4)PPh2] (2). Complex 1 reacts with CO to give RhClCO(PCCl)2 (3). 31P NMR studies reveal that 1 exhibits a fluxional behaviour in solution in the temperature range −50 to 0 °C. The low temperature spectrum is consistent with the formulation RhCl(η2-PCCl)(η1-PCCl). In cyclic voltammetry complex 2 shows two two-electronic reduction processes, at −0.98 and −1.56 V. Electrochemical …
Metal Telluride Clusters Composed of Niobocene Carbonyl, Telluride, and Cobalt Carbonyl Units: Syntheses, Structures, and Reactivity
2000
Abstract: The reaction of [Cp#2NbTe2H] (1#; Cp# = Cp* (C5Me5) or Cp(x) (C5Me4Et)) with two equivalents of [Co2(CO)8] gives a series of cobalt carbonyl telluride clusters that contain different types of niobocene carbonyl fragments. At 0 degrees C, [Cp#2NbTe2CO3(CO)7] (2#) and [Co4Te2(CO)10] (3) are formed which disappear at higher temperatures: in boiling toluene a mixture of [cat2][Co9Te6(CO)8] (5#) (cat= [Cp#2Nb(CO)2]+) and [cat2][Co11Te7(CO)10] (6#) is formed along with [cat][Co(CO)4] (4#). Complexes 6# transform into [cat][Co11Te7(CO)10] (7#) upon interaction with HPF6 or wet SiO2. The molecular structures of 2(Cp(x)), 4(Cp(x)), 5(Cp*), 6(Cp*) and 7(Cp*) have been determined by X-ray cr…
A DFT study of the ionic [2+2] cycloaddition reactions of keteniminium cations with terminal acetylenes
2015
Abstract The molecular mechanism of the ionic [2+2] cycloaddition (I-22CA) reactions of a keteniminium cation (KC) with acetylene and propyne has been investigated using DFT methods at the MPWB1K/6-311G(d,p) level. These I-22CA reactions take place via a two-step mechanism. The first step is the nucleophilic attack of these alkynes on the central carbon of KC, yielding cyclopropene intermediates, while the second step corresponds to the conversion of these intermediates into more stable cyclobuteniminium cations (CCs). The first step is the rate-determining step, while the second step is responsible for the formation of the two regioisomeric CCs experimentally observed in the reaction with …