Studies of Reaction Mechanisms with All-valence Electron Semi-empirical SCF MO Theories. IX. The Role of Tetracyclo[4.2.0.0<SUP>2,8</SUP>0<SUP>5,7</SUP>]oct-3-ene on the Ground State Potential Energy Hypersurfaces of (CH)<SUB>8</SUB> Isomers
スポンサーリンク
概要
- 論文の詳細を見る
Tetracyclo[4.2.0.0<SUP>2,8</SUP>0<SUP>5,7</SUP>]oct-3-ene (<B>1</B>) is estimated by a MINDO MO calculation to be moderately strained. Interaction between the ethylenic π orbital and the Walsh orbitals of the two cyclopropane rings is extensive in the ground state structure of <B>1</B>. The third highest occupied MO is an out-of-phase combination of the ethylenic 2pπ AO's on C<SUB>3</SUB> and C<SUB>4</SUB>, while the corresponding in-phase combination appears in the lower unoccupied MO's. The interconversion between <B>1</B> and bicyclo[4.2.0]octa-2,4,7-triene (<B>2</B>) is a typical symmetryallowed reaction as revealed by a smooth change in bond indices along the reaction coordinates. The isomerization of substituted cyclooctatetraenes <I>via</I> <B>1</B> and <B>2</B> (Eq. (2)) is predicted to be possible at elevated temperatures. The symmetry-allowed degenerate valence isomerization of <B>1</B> (Eq. (3)) is energetically less favorable due to skeletal constraint.
- 公益社団法人 日本化学会の論文
著者
-
Iwamura Hiizu
Department Of Chemistry Faculty Of Science The University Of Tokyo
-
Kihara Hiroshi
Department of Chemistry, Faculty of Scienc, The University of Tokyo
関連論文
- 1P069 Rad53とKi67 FHA domainのフォールディング経路におけるαヘリカルバースト(蛋白質-物性(安定性,折れたたみなど),第48回日本生物物理学会年会)
- 1P-039 Rad53 FHA1ドメインのフォールデイング経路に現れるαヘリカルバースト(蛋白質-物性(安定性,折れたたみなど),第47回日本生物物理学会年会)
- 1P034 Conformational analysis of trigger factor and its mutant(1. Protein structure and dynamics (I),Poster Session,Abstract,Meeting Program of EABS & BSJ 2006)
- 1P107 Helix-rich intermediate of oxidized and reduced proteins on their folding pathway(3. Protein folding and misfolding (I),Poster Session,Abstract,Meeting Program of EABS & BSJ 2006)
- Exploratory and Mechanistic Studies of the Trimerization Reaction of Benzoylacetylenes in the Presence of a Secondary Amine
- Ferromagnetism in Organic Radical Crystal of 4-(p-Chlorobenzylideneamino)-2,2,6,6-tetramethylpiperidin-1-oxyl
- An Organic Ferromagnet with a Tc of 0.4 K. 4-(p-Phenylbenzylideneamino)-2,2,6,6-tetramethylpiperidin-1-oxyl
- A New Organic Ferromagnet: 4-Benzylideneamino-2,2,6,6-tetramethylpiperidin-1-oxyl
- Molecular Ferromagnet, PM[VO(hfac)_2]_2 (PM=pyrimidine, hfac = 1,1,1,5,5,5-hexafluoropenta-2,4-dionate). Ferromagnetic Assembly of Ground High-Spin Molecules
- Brittle Fracture Strength of Welded and Notched Wide Plate Subjected to Prior Cyclic Loading(Collected Papers Published by Staff of Ship Research Institute at societies and Institutions in 1967)
- Crystal Structure Analysis of Phospholipase A_2 from Trimeresurus flavoviridis (Habu Snake) Venom at 1.5 A Resolution
- Scanning X-ray Microscopy of Living and Freeze-Dried Blood Cells in Two Vanadium-Rich Ascidian Species, Phallusia mammillata and Ascidia sydneiensis samea
- Observation of Biospecimens at Cryotemperatures with Soft X-ray Microscope
- Structures and Magnetic Properties of Bis(hexafluoroacetylacetonato)manganese(II) Ligated withN-[3- and 4-(N-tert-Butyl-N-oxyaminophenyl)]imidazole
- Photochemistry of 9-Benzyloxytriptycenes
- Intermolecular Ferromagnetic Interaction of 4-(2-Naphthylmethyleneamino)-2,2,6,6-tetramethylpiperidin-1-oxyl
- Denaturant-induced helix-coil transition of oligopeptides : theoretical and equilibrium studies of short oligopeptides C17 and AK16
- Approaches toward High-Spin Poly[m-(nitrenophenylene)ethynylenes]. Magnetic Interaction in the Oligomers Containing Two, Three, and Five Nitrene Units
- Pyrimidines as Ferromagnetic Exchange Couplers in Dinuclear Oxovanadium(IV) Coplexes
- Remarkable Enhanced of Lipase Catalytic Activity: Combined Effects of Acyl Donor and Thiacrown Ether Additive during Tans-esterification of 5-Phenyl-1-penten-3-ol
- One-Dimensional Ferrimagnetic Chains with Weak Ferromagnetic Interchain Interaction in a 1 : 1 Manganese(II) Bis(hexafluoroacetylacetonate) Complex with Bis[3-tert-butyl-5-(N-oxy-tert-butylamino)phenyl] Nitroxide
- Intramolecular Interaction between Hydroxyl Group and π-Electrons. X. Tertiary Alcohols Related to Phenethyl Alcohol and 3-Buten-1-ol
- Carboxyl Group as a Proton Donor in the Interaction between Hydroxyl Group and π-Electrons
- Intramolecular Interaction between Hydroxyl Group and π-Electrons. XVI. νO-H Absorption Spectra of Aryldimethylcarbinols and Related Compounds
- Restricted rotation involving the tetrahedral carbon. XXVIII. Barriers to rotation about a CX(X=sp3)-C(=O) bond in 9-(1-methoxycarbonyl-1-methylethyl)triptycenes.
- Restricted rotation involving the tetrahedral carbon. XXV. Barriers to exchange between dl and meso forms of 9-(arylmethyl)triptycenes.
- Dynamic NMR as a nondestructive method for the determination of rates of dissociation. V. Proton affinities of p-substituted N,N-dibenzylanilines in aprotic solvents.
- Observation of Dynamic Nuclear Polarization in the Reaction of N,N-Dimethylaniline Oxide with Acetic Anhydride
- Reaction of 4-Picoline N-Oxide with Acetic Anhydride as Studied by Chemically Induced Dynamic 13C Polarization (CIDNP)
- Chemically Induced Nuclear Polarization in the Hydroxylamine Derivatives Obtained by Addition of 1-Cyano-1-methylethyl Radicals
- Dynamic NMR as a nondestructive method for the determination of rates of dissociation. III. Ionic dissociation of .ALPHA.-chlorodibenzyl sulfide.
- Anomeric Effect Involving Carboxyl and Ethynyl Group in Sulfur-Containing Heterocycles
- Studies of Reaction Mechanisms with All-valence Electron Semi-empirical SCF MO Theories. IX. The Role of Tetracyclo[4.2.0.02,805,7]oct-3-ene on the Ground State Potential Energy Hypersurfaces of (CH)8 Isomers
- CIDNP investigation of aminyl radicals formed by thermolysis of triazenes.
- Anomeric Effect in Sulfur Heterocycles Carrying Sulfur Substituents
- N-Isopropylidene- and N-sec-Butylideneanilines. I. Preparation and Characterization
- N-Alkylideneanilines. III. Behavior of N-Isopropylideneanilines in Methanol-d4
- Effects of para-Substituents on the Rates of Inversion of Biphenyl Derivatives. I. 5,7-Dihydrodibenzo[c,e]thiepins
- Nuclear Magnetic Resonance Study of the Effect of the Hydrogen Bond on the Internal Rotation of Biphenyls
- N-Alkylideneanilines. IV. Kinetics and Mechanism for Site-Exchange of the Methyl Groups in N-Isopropylideneanilines
- Mecchanism of the reaction of methoxycarbonylcarbene as revealed by CIDNP. V. Thermal reaction of methyl diazoacetate with benzyl ethers.
- Studies of Reaction Mechanisms by All-valence Electron Semi-Empirical SCF MO Theories. VIII. Electronic Structure and Valence Isomerization of syn- and anti-Tricyclo[4.2.0.02,5]octa-3,7-dienes
- A Theoretical Aspect on the Mechanism of Thermal Dimerization of Cyclooctatetraene
- The Cope Rearrangement of Bridged Homotropilidenes Studied by MINDO Methods