ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Nonapentafulvalene(1) has been prepared by oxidative coupling of sodium cyclopentadienide (6) and sodium cyclononatetraenide (7) with CuCl2 in THF, two-fold deprotonation of cyclopentadienyl-cyclononatetraene 8 to give dianion 16, and oxidative treatment of 16 with CuCl2 (Schemes 2 and 3). Compound 1 is a highly reactive and thermally instable molecule, since valence isomerisation 1 → 17 proceeds easily even at low temperature (the half-life of 1 is ca. 30 min at -15° in CDCl3). NMR investigations show that nonapentafulvalene is an olefinic molecule with strongly alternating bond lengths, its nine-membered ring deviating strongly from planarity. Comparison of the NMR data of 1 with those of a series of sterically similar pentafulvenes 18 and nonafulvenes 19 (Tables 1 and 2) demonstrates that (a) with regard to the pentafulvene unit of 1, the cyclononatetraene ring acts as very weak electron-donating group, while (b) with regard to the nonafulvene unit of 1, the cyclopentadiene ring acts as weak electron-accepting group. So nonapentafulvalene may be regarded as a ‘nonafulvene of inverse π-polarisation’.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19870700106
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