%0 Journal Article %1 Bock.1980b %A Bock, H. %A Kaim, W. %D 1980 %J Journal of the American Chemical Society %K alkene alkene;photoelectron alkene;spin alkylsilylalkyl cation cation;electron cation;hyperconjugation cation;ionization conformation donor potential radical silylalkylated spectra substituent;ESR %N 13 %P 4429--4438 %R 10.1021/ja00533a023 %T Radical ions. 37. Ionization and one-electron oxidation of electron-rich silylalkyl olefins %V 102 %X Trialkylsilylalkyl substituents (R3Si)nC are powerful electron donors, which enormously modify the properties of parent p systems like ethylene, cyclopentadiene, or 1,4-cyclohexadiene. Due to the destabilization of the mol. ground state and the charge delocalization in the corresponding radical cation, the vertical first ionization energies drop down to 7 eV and selective one-electron oxidn. with AlCl3 in CH2Cl2 produces novel silylalkyl radical cations like (R3SiCH2)2C:C(CH2SiR3)2+.bul., stable even at room temp. The photoelectron and the ESR data indicate sCSi/p hyperconjugative interactions, assisted in the sterically overcrowded mols. by fixed optimum conformations with the sCSi bonds colinear with the p system. The ESR coupling consts. indicate considerable spin population in the Me3Si groups. The soln. structure of the radicals and the temp. dependence of their conformations are discussed. [on SciFinder(R)]

@article{Bock.1980b, abstract = {Trialkylsilylalkyl substituents (R3Si)nC are powerful electron donors, which enormously modify the properties of parent \textgreek{p} systems like ethylene, cyclopentadiene, or 1,4-cyclohexadiene. Due to the destabilization of the mol. ground state and the charge delocalization in the corresponding radical cation, the vertical first ionization energies drop down to 7 eV and selective one-electron oxidn. with AlCl3 in CH2Cl2 produces novel silylalkyl radical cations like (R3SiCH2)2C:C(CH2SiR3)2+.bul., stable even at room temp. The photoelectron and the ESR data indicate \textgreek{s}CSi/\textgreek{p} hyperconjugative interactions, assisted in the sterically overcrowded mols. by fixed optimum conformations with the \textgreek{s}CSi bonds colinear with the \textgreek{p} system. The ESR coupling consts. indicate considerable spin population in the Me3Si groups. The soln. structure of the radicals and the temp. dependence of their conformations are discussed. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Bock, H. and Kaim, W.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/207400f4bd5208f22796377c10f15e256/huebleriac}, doi = {10.1021/ja00533a023}, interhash = {7c52f8dee460d89a9cd1d1e26c84099d}, intrahash = {07400f4bd5208f22796377c10f15e256}, issn = {0002-7863}, journal = {Journal of the American Chemical Society}, keywords = {alkene alkene;photoelectron alkene;spin alkylsilylalkyl cation cation;electron cation;hyperconjugation cation;ionization conformation donor potential radical silylalkylated spectra substituent;ESR}, number = 13, pages = {4429--4438}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Radical ions. 37. Ionization and one-electron oxidation of electron-rich silylalkyl olefins}, volume = 102, year = 1980 }