The Electronic Structures of Several Aliphatic Carbonyls. The Effects of Polar Substituents
スポンサーリンク
概要
- 論文の詳細を見る
The electronic structures of several aliphatic carbonyls, X<SUB>2</SUB>CO, CH<SUB>3</SUB>COX, and (XCO)<SUB>2</SUB> (X=H, F, CN, CH<SUB>3</SUB>), have been investigated by the INDO method. Variations in the calculated electron density, the nπ<SUP>*</SUP>-excitation energy, the electron affinity, and the ionization potential with α-X substitution are explained qualitatively in terms of the σ-attracting and π-donating character of F, the π-attracting nature of CN and XCO, and the σ,π-donating property of CH<SUB>3</SUB>. The lowest <SUP>3</SUP>nπ<SUP>*</SUP> excitation energies and ionization potentials calculated by the UHF method are in reasonable agreement with the experimental values in most cases. The partitioning of the total energy suggests that the C–O bonds of X<SUB>2</SUB>CO compounds in the lowest <SUP>3</SUP>nπ<SUP>*</SUP> state and the radical anions derived from them are somewhat longer than those of the parent molecules, primarily because of the decrease in the electron-core attraction. The C–C bonds in some (XCO)<SUB>2</SUB> compounds appear to be cloven as easily as the C–X one on thermal activation and electron impact.
- 公益社団法人 日本化学会の論文
著者
-
Fueno Takayuki
Department of Synthetic Chemistry Kyoto University
-
YONEZAWA Yoshiro
Department of Applied Chemistry, Faculty of Engineering, Osaka City University
-
Yonezawa Yoshiro
Department of Chemistry, Faculty of Engineering Science, Osaka University
-
Fueno Takayuki
Department of Chemistry, Faculty of Engineering Science, Osaka University
関連論文
- Transfer of Dye Monolayers onto Silver Metal Films Formed by Photolysis of Silver Salt of Carboxymethylcellulose
- An Application of the Water/Supercritical CO_2 Microemulsion to a Novel "Microreactor"
- A Consideration of the Q-e Scheme. IV. A Theoretical Approach to Price-Alfrey's Polarity Term
- Computational Studies of the Isomerization Pathways of Isocyanic Acid HNCO.
- Formations of ON(X2.PI., A2.SIGMA.+) in the Reaction of NH(3.SIGMA.-) with NO in Incident Shock Waves.
- A photochemical storage battery with an n-GaP photoelectrode.
- Comparison of the Electronic Spectra of Geometric Isomers. III. β-Substituted Styrenes
- Photoreduction of silver ion in a titanium dioxide suspension.
- Energy conversion and storage in solid-state photogalvanic cells.
- Transmission of Substituent Effects through Oxygen and Sulfur Atoms. I. 1H Chemical Shifts of Ring-substituted Phenyl Vinyl Ethers and Sulfides
- The Relative cis/trans Reactivity in the Hydrochlorination of 1-Arylpropenes
- Photochemical charging of a silver electrode fixed at a titanium dioxide surface.
- Near-infrared photocurrent of a zinc oxide electrode covered with silver atoms.
- The Electronic Structures of Several Aliphatic Carbonyls. The Effects of Polar Substituents
- Catalysis and mechanism of the isomerization of a .DELTA.5-3-keto steroid.
- Modified INDO calculations of the electronic structure of transition metal carbonyl compounds.
- Substituent Effects in the Benzofuran System. III. Cationic Polymerization
- Hartree-Fock-Slater calculations of the ESCA chemical shifts for transition metal atoms.
- Exact Classical-Mechanical Calculation of the Translational-Vibrational Energy Transfer of Energized Anharmonic Diatomic Molecules
- Kinetic study of the thermal decomposition of isocyanic acid in shock waves.
- Transmission of Substituent Effects through the Oxygen and Sulfur Atoms. IV. CNDO/2 Charge Distributions in Vinyl and Divinyl Ethers and Sulfides
- Transmission of Substituent Effects through Oxygen and Sulfur Atoms. III. The Ionization Equilibrium Constants of Ring-substituted cis-β-Phenoxyacrylic Acids
- Electronic configuration analysis of molecular deformations.
- Transmission of Substituent Effects through Oxygen and Sulfur Atoms. II. 13C Chemical Shifts of Ring-Substituted Phenyl Vinyl Ethers and Sulfides
- MINDO/3 calculations of kinetic isotope effects in heterolysis of neopentyl alcohol.
- Thermal decomposition of hydrogen cyanide in shock waves.
- Semiempirical molecular orbital considerations of the electronic structures of transition metal complexes. II. Acetylene- and azo-nickel complexes.
- Substituent Effects on the 13C and 1H Chemical Shifts of 1-Phenyl-1,3-butadiene and Phenylallene
- Carbon-13 NMR Spectra of 1-Arylpropynes and 1-Arylpropenes. Transmission of the Electronic Effects of Substituents through Carbon-Carbon Triple and Double Bonds