Topic
Acetonitrile
About: Acetonitrile is a research topic. Over the lifetime, 11298 publications have been published within this topic receiving 175275 citations. The topic is also known as: cyanomethane & ethyl nitrile.
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TL;DR: The experimental and ab initio dissociation energies of the (H2O)n(CH3CN)mH+ ions are reported in this article, and the experimental energies range from 10−35 kcal/mol.
Abstract: Experimental and ab initio dissociation energies of the (H2O)n(CH3CN)mH+ ions are reported. The experimental energies range from 10–35 kcal/mol. The proton is best stabilized by placing the maximum number of acetonitrile molecules close to the protonated center in such a way that the formation of a network of strong hydrogen bonds is still possible. Other results from this work are: (1) Distinct solvent shells can be distinguished in these complex ions. (2) Mixtures of several isomeric structures are unlikely for n≤4. (3) When a water or an acetonitrile molecule clusters with (H2O)(CH3CN)H+, the proton is transferred from the acetonitrile to the water. (4) Although electrostatic interactions make the dominant contribution to the bonding in these systems, polarization and charge‐transfer effects contribute also. (5) There is a cooperativity effect among the hydrogen bonds that leads to extensive changes in geometry and charge distribution as successive hydrogen bonds are formed. (6) The relative complexati...
80 citations
TL;DR: A practical, convenient, and cheap copper-catalyzed aerobic oxidative coupling of aromatic alcohols and acetonitrile to β-ketonitriles has been developed and unlocks opportunities for markedly different synthetic strategies.
80 citations
TL;DR: In this article, the complex-formation constants of dibenzo-24-crown-8 (DB24C8) with alkali metal ions in acetonitrile and the solubility of DB 24C8 in methanol, acetitrile, and propylene carbonate were determined conductometrically and spectrophotically at 25 °C.
Abstract: Complex-formation constants (KML+) of dibenzo-24-crown-8 (DB24C8) with alkali metal ions in acetonitrile and the solubility of DB24C8 in methanol, acetonitrile, and propylene carbonate were determined conductometrically and spectrophotometrically at 25 °C, respectively. The KML+ value sequences of the alkali metal ions with DB24C8 are Na+>Cs+>K+=Rb+. Dibenzo-24-crown-8 shows no remarkable selectivity for the alkali metal ions in acetonitrile. Transfer activity coefficients of the DB24C8 complexes with alkali metal ions were calculated from these data and literature values of transfer activity coefficients of alkali metal ions. For the same alkali metal ion, the bulky DB24C8-alkali metal ion complex is more soluble in the aprotic solvents acetonitrile and propylene carbonate than in the protic solvent methanol as compared with the case of the alkali metal ion itself. The transfer activity coefficient of the DB24C8-alkali metal ion complex from methanol to acetonitrile is somewhat sensitive to the variation...
80 citations
TL;DR: In this paper, the effect of solvent on the difference in energy between the E and Z rotamers of methyl formate and methyl acetate has been studied using reaction field theory and the spherical cavity approximation.
Abstract: The effect of solvent on the difference in energy between the E and Z rotamers of methyl formate and methyl acetate has been studied using reaction field theory and the spherical cavity approximation. The calculated free energy difference for methyl formate was reduced from 5.2 kcal/mol for e=35.9 (acetonitrile). Similarly, with methyl acetate the difference was reduced from 8.5 to 5.2 kcal/mol. The changes in geometry, dipole moments, charge distributions, and vibrational frequencies on going from e=1 to 35.9 also were calculated and are in accord with increasing polar character of the carbonyl group in the more polar solvent
79 citations
79 citations