𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Non-pentagonal unsaturated dodecahedranes-in-plane delocalized 4C/3e radical cations and σ-bishomoaromatic 4C/2e dications

✍ Scribed by Andreas Weiler; Edith Quennet; Manfred Keller; Kai Exner; Horst Prinzbach

Book ID
104210434
Publisher
Elsevier Science
Year
2000
Tongue
French
Weight
249 KB
Volume
41
Category
Article
ISSN
0040-4039

No coin nor oath required. For personal study only.

✦ Synopsis

An intriguing route from bissecododecahedrenes to 11,17-disubstituted bishomododecahedrene (7) provides access to X-ray crystallographic data (i.e. pyramidalization angle of ca. 22 ). Electrochemical oxidation of the parent ole®n (4, E pc =1.46 V) leads via the bishomododecahedradiene (3, d pp =3.0 A Ê , E 1/2 =0.84 V, E pc =1.67 V) to the in-plane delocalized 4C/3e radical cation (3 + , d pp =2.85 A Ê ) and the s-bishomoaromatic 4C/2e dication (3 2+ , d pp =2.71 A Ê ).

📜 SIMILAR VOLUMES

Secododecahedradienes – Syntheses, React
Secododecahedradienes – Syntheses, Reactivity, in-Plane Homoconjugated 3C/2e Cations, 4C/3e Radical Cations, and σ-Bishomoaromatic 4C/2e Dications?
✍ Jens Reinbold; Martin Bertau; Torsten Voss; Dieter Hunkler; Lothar Knothe; Horst 📂 Article 📅 2001 🏛 John Wiley and Sons 🌐 German ⚖ 583 KB

in alter Verbundenheit (H. P.; H.-D. M.) zum 80. Geburtstag Secodecahedradiene 2a, featuring very proximate, perfectly syn-periplanar and significantly pyramidalized CC bonds, was synthesized as testing object for in-plane(s)-homoconjugational electron delocalization, starting from the available pag

Electrophilic and oxidative chemistry of
Electrophilic and oxidative chemistry of pyrene and its non-alternant isomers: theoretical (DFT, GIAO-NMR, NICS) study of protonation carbocations and oxidation dications from pyrene, azupyrene (dicyclopenta[ef,kl]heptalene) and dicyclohepta[ed,gh]pentaleneElectronic supplementary information (ESI) available: Table S1: Electronic energies (E), zero point energies (ZPE) and Gibbs free energies (G) obtained from DFT calculations for the studied molecules and cations at B3LYP/6-31G(d) level. Figs. S1, S8 and S10 and Tables S2?S14: Optimized structures and Cartesian coordinates for 1, 1aH+, 1bH22+, 12+, 2, 2aH+, 2aH22+, 22+, 3, 3cH+, 3eH22+ and 32+. Figs. S2, S3 and S4: Computed 13C NMR chemical shifts and NPA-derived charges for 1aH+, 122+ and 12+. Fig. S5: Experimental 13C NMR chemical shifts for 1aH+ and 12+. Figs. S6, S7, and S12: HOMO?LUMO forms in the oxidation dications. Figs. S9 and S11: Bond-lengths in X-ray derived and computed structures for 2 and 3. See http://www.rsc.org/suppdata/ob/b4/b405009f/
✍ Okazaki, Takao; Laali, Kenneth K. 📂 Article 📅 2004 🏛 Royal Society of Chemistry 🌐 English ⚖ 409 KB