21517-94-2Relevant academic research and scientific papers
ESR Study of 2-Substituted 2-Adamantyl Radicals. Configuration and Long-Range Hyperfine Interaction.
Kira, Mitsuo,Akiyama, Mieko,Ichinose, Michiko,Sakurai, Hideki
, p. 8256 - 8262 (1989)
Structure and long-range hyperfine interaction in 2-adamantyl, 5,7-dimethyl-2-adamantyl, and the various 2-substituted radicals (substituent = CH3, CH2SiMe3, OSiMe3, SSiMe3, CH2GeMe3, etc.) were studied by ESR.The origin of the long-range hyperfine interaction is discussed on the basis of the comparison between experimental and theoretical hfs values.The pyramidality of the radical center by a proper substituent at the 2-position of 2-adamantyl radicals has been found to exert significant influence to the long-range interaction.The analyses of hfs values for persistent 2-bis( trimethylsilyl)methyl-2-adamantyl radical and the 5,7-dimethyl derivative were made by the assistance of the ENDOR spectrum.The very small hfs values observed for the bis(trimethylsilyl)methyl methine protons not only show almost perpendicular arrangement of the Cα-Hβ bond to the singly occupied p? orbital but also suggest that the constant A in the Heller-McConnell equation would be positive on the basis of the positive temperature dependence.
Photochemically Induced Hydrogen Abstraction by Carbon Radicals in an Adamantane Matrix: Generation and Photochemical Cleavage of 2-Adamantyl Radicals
Korth, Hans-Gert,Lange, Fritz,Luebbe, Fritz,Mueller, Wolfgang,Seidel, Margret,Sustmann, Reiner
, p. 1293 - 1298 (2007/10/02)
Matrix-isolated cyclic allylic and 1-adamantyl radicals are activated by u.v. radiation to abstract hydrogen or deuterium atoms from the matrix material adamantane and adamantane, as is observed by e.s.r. spectroscopy.The 2-adamantyl or 2-adamantyl radicals thus formed, undergo a further photochemically induced cleavage reaction, interpreted in terms of a β-CC scission to the (7-bicyclonon-2-enyl)methyl or (7-bicyclonon-2-enyl)methyl radicals, respectively.From the latter radicals, the 2-adamantyl (2-adamantyl) radicals are regenerated in the dark, presumably by both intramolecular addition and intermolecular hydrogen (deuterium) abstraction from the matrix.
