121-46-0Relevant articles and documents
SURFACE PHOTOCHEMISTRY: SEMICONDUCTOR PHOTOINDUCED VALENCE ISOMERIZATION OF QUADRICYCLANE TO NORBORNADIENE
Draper, Anthony M.,Mayo, Paul de
, p. 6157 - 6160 (1986)
Contrary to a recent report, the valence isomerization via a radical cation, of quadricyclane to norbornadiene on the surface of illuminated CdS and ZnO is described.
Iridium-Catalyzed Asymmetric Hydroalkenylation of Norbornene Derivatives
Sun, Xin,Bai, Xiao-Yan,Li, An-Zhen,Li, Bi-Jie
, p. 2182 - 2187 (2021)
Transition-metal-catalyzed asymmetric hydroalkenylation of alkenes provides an atom-economical method to build molecular complexity from easily available materials. Herein we report an iridium-catalyzed asymmetric hydroalkenylation of unconjugated alkenes with acrylamides and acrylates. The catalytic hydroalkenylation of norbornene derivatives occurred to form products with allylic stereocenters with high chemo-, regio-, and stereoselectivities. DFT calculations revealed that the migratory insertion is irreversible and the enantiodetermination step.
DIOXIRANES: DIMETHYLDIOXIRANE CATALYZED VALENCE ISOMERIZATION OF QUADRICYCLANE
Murray, Robert W.,Pillay, M. Krishna
, p. 15 - 18 (1988)
Dimethyldioxirane, 3, catalyzes the isomerization of quadricyclane to norbornadiene.Turnover numbers up to 60 have been measured.The unusual orbital occupancy in 3 may be responsible for these observations.
Structure-Reactivity Factors for Exciplex Isomerization of Quadricyclene and Related Compounds
Jones, Guilford,Chiang, Sheau-Hwa,Becker, William G.,Greenberg, Don P.
, p. 681 - 683 (1980)
The quadricyclenes (1) and (3) are equally effective in exciplex isomerization although other cage hydrocarbons do not undergo efficient reaction when sensitized by aromatic fluorophores; irradiation of charge-transfer complexes of (1) and (3) and electron-deficient alkenes results in efficient valence but not geometrical isomerization.
Electron transfer induced deazatization of cyclic Azo derivatives of quadricyclane and norbornadiene
Sluggett, Gregory W.,Turro, Nicholas J.,Roth, Heinz D.
, p. 9982 - 9989 (1995)
The photosensitized oxidation of two cyclic azoalkane derivatives (Azo-Q, Azo-N) of quadricyclane (Q) and norbornadiene (N) has been investigated using steady-state and laser flash photolysis techniques as well as chemically induced dynamic nuclear polarization (CIDNP). Irradiation of acetonitrile solutions of 9,10-dicyanoanthracene (DCA), 2,6,9,10-tetracyanoanthracene (TCA), or chloranil (Chl) in the presence of Azo-Q results in rapid and efficient deazatization to afford N. Similar irradiation of DCA, TCA, and Chl in the presence of Azo-N yields N and Q. CIDNP experiments reveal that polarized N is formed as a cage product in the Chl sensitized photolysis of Azo-Q while polarized N and Q are both formed as cage products from Azo-N. The results are consistent with competitive fragmentation of Azo-N?+ to N?+ and Q?+, and selective deazatization of Azo-Q?+ to N?+. Irradiation of 1-cyanonaphthalene in the presence of Azo-Q or Azo-N affords Q and/or N in chemical yields similar to those obtained from direct and naphthalene sensitized irradiations, indicative of singlet energy transfer quenching. Bimolecular rate constants for quenching by Azo-N and Azo-Q were determined by steady-state fluorescence methods for singlet sensitizers, or by laser flash photolysis (LFP) for 3Chl*.
THERMAL ISOMERIZATION OF QUADRICYCLANE TO NORBORNADIENE CATALYZED BY COPPER(II) AND TIN(II) SALTS.
Fife,Morse,Moore
, p. 7404 - 7407 (1983)
Copper(II) salts and tin(II) chloride show exceptional heterogeneous catalytic behavior in converting quadricyclane to norbornadiene in benzene. The heterogeneous catalysis mechanism is described by the adsorption of quadricyclane on the salt surface by a combination of a one-site and a two-site coordination. The two-site-coordination process results in the formation of C//7H//8X//2 (X equals Cl or Br) as a side product when CuCl//2 or CuBr//2 are used as catalysts. The rate constant for the disappearance of quadricyclane is much greater when CuCl//2 or CuBr//2 are used as catalysts. The rate constant for the disappearance of quadricyclane is much greater when CuCl//2 or CuBr//2 (approximately 10** minus **2 min** minus **1 cm** minus **2) is used than when CuSO//4 (approximately 10** minus **4 min** minus **1 cm** minus **2) is used.
PHOTOISOMERIZATION OF NORBORNADIENE TO QUADRICYCLANE IN THE PRESENCE OF COPPER(I)-NITROGEN LIGAND CATALYSTS
Maruyama, Kazuhiro,Terada, Kazutoshi,Naruta, Yoshinori,Yamamoto, Yoshinori
, p. 1259 - 1262 (1980)
Use of copper(I)-nitrogen ligand catalysts, such as Ph3PCuCl.bipy (1), Ph3PCuCl.phen (2), Ph3PCuCl.phtha (3), and Ph3PCuBr.py (4), enables the photochemical isomerization of norbornadiene to quadricyclane in longer wavelength than 350 nm, in which CuCl catalyst itself can not induce such an isomerization.
PHOTOGENERATED CATALYSIS BY TRANSITION-METAL COMPLEXES. PHOTOACCELERATION OF THE VALENCE ISOMERIZATION OF QUADRICYCLENE TO NORBORNADIENE IN THE PRESENCE OF PdCl2( eta 4-NORBORNADIENE).
Borsub,Kutal
, p. 4826 - 4828 (1984)
Light accelerates the rate at which PdCl//2( eta **4-NBD) (1) catalyzes the valence isomerization of quadricyclene (Q) to norbornadiene (NBD). The observed quantum yield, defined as (mol of NBD produced/mol of photons absorbed), can exceed 10**2 and is dependent upon Q concentration, light intensity, and solvent. Several lines of evidence are consistent with the intermediacy of radical species in the isomerization process. The results are discussed in terms of a redox-chain mechanism in which the initiation step involves reductive quenching of a Pd-to-NBD charge-transfer excited state of 1 by Q.
Organic Photochemistry with 6.7 eV Photons: Tetracyclo2,7.04,6>heptane (Quadricyclene)
Srinivasan, Ra.,Baum, Thomas,Epling, Gary
, p. 437 - 438 (1982)
Irradiation of quadricyclene in solution leads to isomeric products in addition to bicyclohepta-2,5-diene, which reduces its usefulness in solar energy storage.
Chemistry of Weakly Solvated Lanthanide-Metal Cations. Synthesis, Characterization, and Catalytic Chemistry of x
Thomas, Richard R.,Chebolu, Venkatasuryanarayana,Sen, Ayusman
, p. 4096 - 4103 (1986)
The title compound, x, 1, was synthesized by the NOBF4 oxidation of metallic Eu in CH3CN.The interaction of the BF4- ions with the Eu(III) center was established by molecular weight, conductivity, and 11B and 19F NMR spectral measurements. 1 was found to exist as a dimer in CH3CN.In addition, it behaved as a 1:2 electrolyte, indicating the coordination of two of the BF4- ions per Eu(III) ion.However, the conductivity increased when chelating amines were added due to the partial displacement of the coordinated BF4- ions.The 11B and 19F NMR spectra of 1 in CH3CN indicated the presence of two different types of BF4- anions, one of which was isotropically shifted due to interaction with the paramagnetic Eu(III) center.The coordinated BF4- anions could be displaced quantitatively by the addition of 2 equiv of NO3- ions per Eu(III) ion.A degenerate metathesis of the fluorine between the BF3 and the coordinated BF4- ions was observed when BF3 was added to a CH3CN solution of 1. 1 formed a charge-transfer complex with tetra-p-anisylethylene in CH3NO2 but not in CH3CN.In addition, 1 initiated the oligomerization and the polymerization of styrene, α-methylstyrene, and 1,3-cyclohexadiene in CH3NO2.The molecular weights of the polymers obtained increased markedly on lowering the reaction temperature.At room temperature, indan derivatives were obtained from α-methyl- and α-phenylstyrene.The rate of polymerization of styrene was markedly attenuated when CH3CN was used instead of CH3NO2. 1 also initiated the isomerization of quadricyclane and the ring-opening polymerization of 2(10)-pinene and cyclopropylbenzene in CH3NO2.
