ISSN:
0009-2940
Keywords:
Silicon compounds
;
Sterically overcrowded organosilicon molecules
;
Photoelectron and ESR spectra of radical cations
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Structures and Molecular Properties of Sterically Overcrowded Molecules, 36[1]. - (E)-1,1,1,4,4,4-Hexakis(trimethylsilyl)-2-butene [(H3C)3Si]3C - HC=CH - C[Si(CH3)3]3 and Bis[tris(trimethylsilyl)silyl]ethin [(H3C)3Si]3Si - C≡C - Si[Si(CH3)3]3The single crystal structure of an ethylene derivative, in which the two substituent half-shells are separated by a C=C spacer of about 403 pm length, shows C≡C distances of 404, 415 as well as 421 pm between non-adjacent and of 352 pm between adjacent methyl groups, i.e. close to or within their van der Waals radii sum of 400 pm. The PE-spectroscopically determined vertical first ionization energies of both compounds, 7.78 eV and 7.71 eV, are each the lowest ones reported so far for disubstituted ethylenes and acetylenes. Despite of irreversible cyclovoltammetric oxidation potentials, the radical cation of the six-fold R3Si-substituted 2-butene can be generated by SbCl5/H2CCl2 and characterized below 230 K by its ESR spectrum.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931261010
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