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Volumn , Issue 3, 2008, Pages 435-443

Photochemical generation and structure of vinyl radicals

Author keywords

Ab initio calculations; Photochemistry; Stereoselectivity; Structure elucidation; Vinyl radicals

Indexed keywords


EID: 38849102999     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200700882     Document Type: Article
Times cited : (39)

References (57)
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    • C. Galli, A. Guarnieri, H. F. Koch, P. Mencarelli, Z. Rappoport, J. Org. Chem. 1997, 62, 4072-4077. The vinyl radicals with α-substituents H, Cl and F were also calculated at the higher level B3LYP/6-311G(2d,2p).
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    • G. Lodder, chapter 8 in Dicoordinated Carbocations (Eds.: Z. Rappoport, P. J. Stang), Wiley, West Sussex, 1997;
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    • P. J. Kropp, chapter 84 in CRC Handbook of Organic Photochemistry and Photobiology (Eds.: W. M. Horspool, P.-S. Song), CRC Press, Boca Raton, 1995;
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    • T. Kitamura, chapter 85 in CRC Handbook of Organic Photochemistry and Photobiology (Eds.: W. M. Horspool, P.-S. Song), CRC Press, Boca Raton, 1995;
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    • [17,16,18]. where the points of focus are the cation-derived products.
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    • In the presence of oxygen, next to c and d, other vinyl radical-derived products are produced. See: J. M. Verbeek, M. Stapper, E. S. Krijnen, J.-D. Van Loon, G. Lodder, S. Steenken, J. Phys. Chem. 1994, 98, 9526-9536
    • In the presence of oxygen, next to c and d, other vinyl radical-derived products are produced. See: J. M. Verbeek, M. Stapper, E. S. Krijnen, J.-D. Van Loon, G. Lodder, S. Steenken, J. Phys. Chem. 1994, 98, 9526-9536.
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    • A trace amount of Ph-C≡C-F is produced via β-proton loss from the vinylic cation
    • A trace amount of Ph-C≡C-F is produced via β-proton loss from the vinylic cation.
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    • The C-H bond dissociation energies of ethene and methanol are 108 and 92.6 kcal/mol, respectively, according to: K. W. Egger, A. T. Cocks, Helv. Chim. Acta 1973, 56, 1516-1536.
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    • [10] plot final concentration ratios instead of reaction rate ratios. Care must be taken, however, to avoid free radical induced cis/trans isomerization or, in the case of photochemical approaches, photochemical isomerization;
    • [10] plot final concentration ratios instead of reaction rate ratios. Care must be taken, however, to avoid free radical induced cis/trans isomerization or, in the case of photochemical approaches, photochemical isomerization;
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    • The difference in activation enthalpy for an exothermic radical scavenging will be mainly composed of the difference in steric repulsion for cis and trans attack, which follows from the Bell-Evans-Polanyi principle.
    • The difference in activation enthalpy for an exothermic radical scavenging will be mainly composed of the difference in steric repulsion for cis and trans attack, which follows from the Bell-Evans-Polanyi principle.
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    • The vibrational contribution to the molecular partition function, and thus to the entropy is usually the largest. The normal modes of a molecule, in turn, are determined by symmetry; cf., for instance, P. W. Atkins, Physical Chemistry, Oxford University Press, Oxford, 1995, 5th edition, chapters 16, 19 and 20.
    • The vibrational contribution to the molecular partition function, and thus to the entropy is usually the largest. The normal modes of a molecule, in turn, are determined by symmetry; cf., for instance, P. W. Atkins, Physical Chemistry, Oxford University Press, Oxford, 1995, 5th edition, chapters 16, 19 and 20.
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    • Irradiation of 5a yields Ph-C≡C-C≡C-H and Ph-C(H)=C=C=C(H)-Br (tentative structure), produced from the vinylic cation by β-proton loss and 1,3-bromide shift, respectively.
    • Irradiation of 5a yields Ph-C≡C-C≡C-H and Ph-C(H)=C=C=C(H)-Br (tentative structure), produced from the vinylic cation by β-proton loss and 1,3-bromide shift, respectively.
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