Structural effects of different NH-acids and dialkyl acetylenedicarboxylates on the kinetic parameters of stable phosphorus ylids: a mechanistic investigation

Kinetic studies were made of the reactions between triphenylphosphine 1 and dialkyl acetylenedicarboxylates 2, in the presence of NH-acids, such as benzotriazole, 5-methylbenzotriazole or 5-chlorobenzotriazole 3 (as a protic/nucleophilic reagent). To determine the kinetic parameters of the reactions, they were monitored by UV spectrophotometry. Useful information was obtained from studies of the effect of solvent, structure of reactants (dialkyl acetylenedicarboxylates and NH-acids) and also concentration of reactants on the reaction rates. First and third steps (k 2 , k 3 ) of all reactions were recognized as a rate determining and fast steps, respectively. Proposed mechanism was confirmed on the basis of experimental data

Theoretical study of interaction of NH₂X (X = H, CH₃, CH₂OCH₃, and CH₂COOH) molecules with AlN and AlP nanotubes

<p></p> <p>In this work, we have studied the interaction of NH₃, NH₂CH₃, NH₂CH₂OCH₃, and NH₂CH₂COOH with aluminum nitride (AlN) and aluminum phosphide (AlP) nanotubes (NT) by means of the B3LYP hybrid density functional method using 6-31G(d) basis set. The results show that these molecules can be chemically adsorbed on the top of the aluminum atom of AlNNTs and AlPNTs. Also, the AlP nanotubes are the most energetically favorable candidates for adsorption of these molecules. It was found that the interaction these molecules with nanotubes results in changes in the electronic properties of NTs. Based on the NBO analysis, in all complexes charge transfer occurs from these molecules to nanotubes. The AIM results show that, the Al…N interaction has a partial covalent nature. Also, this interaction in the AlP complexes is stronger than that in the AlN complexes. In both types of complexes, the results obtained for complexes containing electron-donating molecules are better than complexes containing electron-withdrawing ones.</p

Structural effects of different NH-acids and dialkyl acetylenedicarboxylates on the kinetic parameters of stable phosphorus ylids: a mechanistic investigation

Kinetic studies were made of the reactions between triphenylphosphine 1 and dialkyl acetylenedicarboxylates 2, in the presence of NH-acids, such as benzotriazole, 5-methylbenzotriazole or 5-chlorobenzotriazole 3 (as a protic/nucleophilic reagent). To determine the kinetic parameters of the reactions, they were monitored by UV spectrophotometry. Useful information was obtained from studies of the effect of solvent, structure of reactants (dialkyl acetylenedicarboxylates and NH-acids) and also concentration of reactants on the reaction rates. First and third steps (k2, k3) of all reactions were recognized as a rate determining and fast steps, respectively. Proposed mechanism was confirmed on the basis of experimental data