544-25-2Relevant articles and documents
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Anastassiou,Cellura
, p. 1521 (1969)
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Pulse Radiolysis Study of the Cycloheptatriene Triplet State: Lifetime, Relaxation, and Nonvertical Excitation
Gorman, A. A.,Hamblett, I.,Irvine, M.,Raby, P.,Standen, M. C.,Yeates, S.
, p. 4404 - 4411 (1985)
The triplet state of cycloheptatriene (CHT) has been produced by pulse radiolysis in toluene.Its lifetime of 6 +/- 1 μs is considerably longer than for acyclic trienes, ca. 300 ns, despite a smaller energy gap between the relaxed T1 and S0 surfaces.It is proposed that relaxation is from the boatlike spectroscopic state to an approximately planar species within which spin-orbit coupling factors are minimized.Plots of log ket vs. donor triplet energy for endothermic triplet energy transfer to both CHT and the acyclic neo-alloocimene (NA) show that, whereas the latter is close to being a vertical acceptor of triplet energy, CHT exhibits clear "nonvertical" character.In this respect, NA and CHT mimic trans- and cis-stilbene, respectively.It would appear that, for olefinic systems, established "nonvertical" behavior is currently restricted to nonplanar ? systems, and the possibility is raised that such behavior may, at least in part, reflect higher vibrational level densities in such systems.
Photolysis of two tricyclic nonenediones. Direct observation of norcaradiene
Rubin, Mordecai B.
, p. 7791 - 7792 (1981)
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Synthesis of 1,2,3,4,5,6,7-Heptasubstituted Cycloheptatrienes through Cycloaddition Reactions of Substituted Cyclopentadienones
Platonov, Dmitry N.,Belyy, Aleksandr Yu.,Ananyev, Ivan V.,Tomilov, Yury V.
, p. 4105 - 4110 (2016)
Two schemes for synthesizing heptasubstituted cycloheptatrienes with various substituents in the ring are suggested. The first method is based on cycloaddition of 2,5-dimethoxycarbonyl-3,4-diphenylcyclopentadienone with substituted cyclopropenes and allows cycloheptatrienes containing two or three electron-withdrawing substituents in the molecule to be obtained. The second method employs a cascade reaction between a substituted cyclopentadienone and appropriate vinyldiazoacetates. It allows the number of electron-withdrawing substituents to be increased to five. In all cases, heptasubstituted cycloheptatrienes are formed as just one of the possible isomers.
Synthesis and characterization of manganese triple-decker complexes
Heinl, Sebastian,Balázs, Gábor,Bodensteiner, Michael,Scheer, Manfred
, p. 1962 - 1966 (2016)
The use of the highly sterically demanding CpBIG ligand (CpBIG = C5(4-nBuC6H4)5) and white phosphorus (P4) enables the synthesis of new P-rich derivatives of the rare Pn ligand complexes of manganese. The obtained complexes, [{CpBIGMn}2(μ,η5:5-P5)] (2) and [{CpBIGMn}2(μ,η2:2-P2)2] (3), exhibit the highest number of P atoms in this class of manganese compounds identified by X-ray structure analyses. The EPR spectrum of the 29 VE triple-decker complex 2 shows one unpaired electron coupling with two 5/2 spin Mn nuclei.
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Gassman,P.G.,Creary,X.
, p. 2729 - 2731 (1973)
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Gold Catalysts Can Generate Nitrone Intermediates from a Nitrosoarene/Alkene Mixture, Enabling Two Distinct Catalytic Reactions: A Nitroso-Activated Cycloheptatriene/Benzylidene Rearrangement
Cheng, Mu-Jeng,Kardile, Rahul Dadabhau,Kuo, Tung-Chun,Liu, Rai-Shung,More, Sayaji Arjun
supporting information, p. 5506 - 5511 (2021/07/31)
Gold-catalyzed reactions of cycloheptatrienes with nitrosoarenes yield nitrone derivatives efficiently. This reaction sequence enables us to develop gold-catalyzed aerobic oxidations of cycloheptatrienes to afford benzaldehyde derivatives using CuCl and nitrosoarenes as co-catalysts (10-30 mol %). Our density functional theory calculations support a novel nitroso-activated rearrangement, tropylium → benzylidene. With the same nitrosoarenes, we developed their gold-catalyzed [2 + 2 + 1]-annulations between nitrosobenzene and two enol ethers to yield 5-alkoxyisoxazolidines using 1,4-cyclohexadienes as hydrogen donors.
Gold(I) Carbenoids: On-Demand Access to Gold(I) Carbenes in Solution
Sarria Toro, Juan M.,García-Morales, Cristina,Raducan, Mihai,Smirnova, Ekaterina S.,Echavarren, Antonio M.
supporting information, p. 1859 - 1863 (2017/02/05)
Chloromethylgold(I) complexes of phosphine, phosphite, and N-heterocyclic carbene ligands are easily synthesized by reaction of trimethylsilyldiazomethane with the corresponding gold chloride precursors. Activation of these gold(I) carbenoids with a variety of chloride scavengers promotes reactivity typical of metallocarbenes in solution, namely homocoupling to ethylene, olefin cyclopropanation, and Buchner ring expansion of benzene.