%0 Journal Article %1 Bock.1979 %A Bock, H. %A Kaim, W. %A Kira, M. %A West, R. %D 1979 %J Journal of the American Chemical Society %K ESR ESR;ionization ESR;photoelectron MO;oxidn cyclopentasilane cyclopoly cyclopolysilane deriv;silane permethyl permethylcyclopolysilane permethylcyclopolysilane;permethylcyclopolysilane potential radical spectrum %N 26 %P 7667--7670 %R 10.1021/ja00520a006 %T Novel organosilicon radical cations. One-electron oxidation of permethylcyclopolysilanes %V 101 %X The permethylcyclosilanes I R = Me (II), R2 = SiMe2SiMe2 (III), IV and V, all of which exhibit low 1st ionization potentials, were oxidized with AlCl3 in CH2Cl2 to form the 1st examples of delocalized, s-electron radical cations, which were studied by ESR spectroscopy. Unlike the well-known radical anion of II, the radical cation gives an ESR spectrum which can be simulated only by assuming 2 sets of 18 equiv. protons, corresponding to 6 axial and 6 equatorial Me groups which do not become equiv. on the ESR time scale. The high g value of 2.0093 obsd. for the radical cation suggests a considerable spin population in the Si6 ring skeleton. The radical cations of III, IV and V show only overlapping signals in the ESR, but their resp. g values of 2.010, 2.0105 and 2.0063 are also consistent with spin delocalization into the sSi-Si system. on SciFinder(R)

@article{Bock.1979, abstract = {The permethylcyclosilanes I [R = Me (II), R2 = SiMe2SiMe2 (III)], IV and V, all of which exhibit low 1st ionization potentials, were oxidized with AlCl3 in CH2Cl2 to form the 1st examples of delocalized, \textgreek{s}-electron radical cations, which were studied by ESR spectroscopy. Unlike the well-known radical anion of II, the radical cation gives an ESR spectrum which can be simulated only by assuming 2 sets of 18 equiv. protons, corresponding to 6 axial and 6 equatorial Me groups which do not become equiv. on the ESR time scale. The high g value of 2.0093 obsd. for the radical cation suggests a considerable spin population in the Si6 ring skeleton. The radical cations of III, IV and V show only overlapping signals in the ESR, but their resp. g values of 2.010, 2.0105 and 2.0063 are also consistent with spin delocalization into the \textgreek{s}Si-Si system. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Bock, H. and Kaim, W. and Kira, M. and West, R.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/20c728207ab0839636e69629dc167434a/huebleriac}, doi = {10.1021/ja00520a006}, interhash = {b4b86a6c16e9ddf169e24f5a079a3d2e}, intrahash = {0c728207ab0839636e69629dc167434a}, issn = {0002-7863}, journal = {Journal of the American Chemical Society}, keywords = {ESR ESR;ionization ESR;photoelectron MO;oxidn cyclopentasilane cyclopoly cyclopolysilane deriv;silane permethyl permethylcyclopolysilane permethylcyclopolysilane;permethylcyclopolysilane potential radical spectrum}, number = 26, pages = {7667--7670}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Novel organosilicon radical cations. One-electron oxidation of permethylcyclopolysilanes}, volume = 101, year = 1979 }