| Literature DB >> 10813951 |
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Abstract
Assessment of the cyclic electron delocalization of the oxocarbon dianions, C(n)()O(n)()(2)(-) and their neutral counterparts C(n)()O(n)() (n = 3-6), by means of structural, energetic, and magnetic criteria, shows that C(3)O(3)(2)(-) is doubly aromatic (both sigma and pi cyclic electron delocalization), C(4)O(4)(2)(-) is moderately aromatic, but C(5)O(5)(2)(-), as well as C(6)O(6)(2)(-), are less so. Localized orbital contributions, computed by the individual gauge for localized orbitals method (IGLO), to the nucleus-independent chemical shifts (NICS) allow pi effects to be disected from the sigma single bonds and other influences. The C-C(pi) contribution to (NICS(0,pi) (i.e., at the center of the ring) in oxocarbon dianions decreases with ring size but shows little ring size effect at points 1.0 A above the ring. On the basis of the same criteria, C(4)O(4) exhibits cyclic electron delocalization due to partial occupancy of the sigma CC bonds. However, the dissociation energies of all the neutral oxocarbons, C(n)()O(n)(), are highly exothermic.Year: 2000 PMID: 10813951 DOI: 10.1021/jo991267n
Source DB: PubMed Journal: J Org Chem ISSN: 0022-3263 Impact factor: 4.354