%0 Journal Article %1 Bock.1980c %A Bock, H. %A Kaim, W. %A Noeth, H. %A Semkow, A. %D 1980 %J Journal of the American Chemical Society %K ESR aluminum cation chloride conformation coupling potential radical silylhydrazine silylhydrazine;MO silylhydrazine;hypersurface silylhydrazine;ionization silylhydrazine;isotropic silylhydrazine;oxidn silylhydrazine;photoelectron silylhydrazine;radical spectra %N 13 %P 4421--4428 %R 10.1021/ja00533a022 %T Radical ions. 36. Structural changes accompanying the one-electron oxidation of hydrazine and its silyl derivatives %V 102 %X (Me3Si)2NN(SiMe3)2, I, and II are ionized in the gas phase and oxidized in soln. The photoelectron spectroscopically detd. vertical ionization energies of the N atom lone pairs provide information on the ground-state geometry. Oxidn. with AlCl3 in CH2Cl2 adiabatically produces radical cations, for which ESR reveals stabilizing structural changes: the perpendicular Me3SiN halves of the open-chain mol. twist toward planarity, and the chair conformation of the 6-membered ring turns into half-chair by flattening of one SiNNSi link. These observations., as well as literature data on B-, C-, or P-substituted hydrazine radical cations, are rationalized by a geometry-optimized INDO open-shell hypersurface for the parent ion N2H4+.bul., according to which one-electron oxidn. should planarize the tetrasubstituted NN+.bul. fragment skeleton and shorten the N-N bond length by $\sim$25 pm. In addn., three-dimensional tables of INDO 14N and 1H coupling consts. allow comparative ests. of the structural changes during the oxidn. of hydrazine derivs. in soln. [on SciFinder(R)]

@article{Bock.1980c, abstract = {(Me3Si)2NN(SiMe3)2, I, and II are ionized in the gas phase and oxidized in soln. The photoelectron spectroscopically detd. vertical ionization energies of the N atom lone pairs provide information on the ground-state geometry. Oxidn. with AlCl3 in CH2Cl2 adiabatically produces radical cations, for which ESR reveals stabilizing structural changes: the perpendicular Me3SiN halves of the open-chain mol. twist toward planarity, and the chair conformation of the 6-membered ring turns into half-chair by flattening of one SiNNSi link. These observations., as well as literature data on B-, C-, or P-substituted hydrazine radical cations, are rationalized by a geometry-optimized INDO open-shell hypersurface for the parent ion N2H4+.bul., according to which one-electron oxidn. should planarize the tetrasubstituted NN+.bul. fragment skeleton and shorten the N-N bond length by $\sim$25 pm. In addn., three-dimensional tables of INDO 14N and 1H coupling consts. allow comparative ests. of the structural changes during the oxidn. of hydrazine derivs. in soln. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Bock, H. and Kaim, W. and Noeth, H. and Semkow, A.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2b7210f58aafd82da3e11c66450aa65bf/huebleriac}, doi = {10.1021/ja00533a022}, interhash = {9df424885a8e04ac45827d9075f23424}, intrahash = {b7210f58aafd82da3e11c66450aa65bf}, issn = {0002-7863}, journal = {Journal of the American Chemical Society}, keywords = {ESR aluminum cation chloride conformation coupling potential radical silylhydrazine silylhydrazine;MO silylhydrazine;hypersurface silylhydrazine;ionization silylhydrazine;isotropic silylhydrazine;oxidn silylhydrazine;photoelectron silylhydrazine;radical spectra}, number = 13, pages = {4421--4428}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Radical ions. 36. Structural changes accompanying the one-electron oxidation of hydrazine and its silyl derivatives}, volume = 102, year = 1980 }