Publications by authors named "Emmerich Sackers"
As part of a study to achieve selective oligo(poly)bromination-ultimately perbromination-of the dodecahedral C(20) skeleton, the extent and direction of the ionic bromination of dodecahedrene and 1,16-dodecahedradiene were explored. Along sequences of Br(+) additions/deprotonations and allylic rearrangements, up to ten hydrogen atoms were substituted (traces of C(20)H(x)Br(10)). Tetrabromododecahedrenes obtained under defined conditions in up to 50 % total yield with three and four allylic bromine substituents protecting the extremely bent C==C bonds, proved highly unreactive even towards oxygen but reacted rapidly with CH(2)N(2).
View Article and Find Full Text PDF"One-pot" substitution of the twenty hydrogen atoms in pentagonal dodecahedrane (C(20)H(20)) by OH, F, Cl, and Br atoms is explored. Electrophilic insertion of oxygen atoms with DMDO and TFMDO as oxidizing reagents ended, far off the desired C(20)(OH)(20), in complex polyol mixtures (up to C(20)H(10)(OH)(10) decols, a trace of C(20)H(OH)(19)?). Perfluorination was successful in a NaF matrix but (nearly pure) C(20)F(20) could be secured only in very low yield.
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- The compounds 1,4,16-dodecahedratriene (4) and 1,4,10(14),16-dodecahedratetraene (5) are unique cage olefins with interesting properties related to their internal structure.
- DFT calculations provide insights into the effects of one- and two-electron oxidation and reduction on the energetics and geometry of compound 5.
- Efforts to synthesize these compounds using specific thermal reactions were unsuccessful, but their anions and cations can be generated through electron impact or ionization, though challenges in mass-selection were encountered due to low ion intensity and structural instability.