Unsaturated dodecahedranes--in quest of the C20H14 1,4,16-triene and C20H12 1,4,10(14),16-tetraene, and their cations and anions.
The highly pyramidal, highly strained 1,4,16-dodecahedratriene (4) and C20H12 1,4,10(14),16-dodecahedratetraene (5) are cage olefins with an intriguing "inner life". For 5 DFT calculations give information about the energetic and geometrical consequences of one-/two-electron oxidation and reduction. Attempts to prepare 4 and 5 through thermal retro[2+2]/[4+2]cycloaddition strategies proved unsuccessful. Still, the C20H14/C20H12 cage cations and anions are liberated upon electron impact or gas-discharge ionization of their thermally extremely stable tris-/tetrakisanthraceno-anellated derivatives. Mass-selection (photoelectron (PE) characterization) of the anions failed, however, due to the very small anion intensity, the preferential formation of hydrogen-poor ions, and minor cage disruption.
Reinbold
Jens
J
Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität, Freiburg, Germany.
Sackers
Emmerich
E
Osswald
Thomas
T
Weber
Klaus
K
Weiler
Andreas
A
Voss
Torsten
T
Hunkler
Dieter
D
Wörth
Jürgen
J
Knothe
Lothar
L
Sommer
Frank
F
Morgner
Nina
N
von
Issendorff Bernd
IB
Prinzbach
Horst
H