Literature DB >> 10813951

Are oxocarbon dianions aromatic?

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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


  3 in total

1.  Theoretical studies on all-metal binuclear sandwich-like complexes M2(η 4-E 4) 2 (M=Al, Ga, In; E=Sb, Bi).

Authors:  Congzhi Wang; Xiuhui Zhang; Jian Lu; Qianshu Li
Journal:  J Mol Model       Date:  2012-02-16       Impact factor: 1.810

2.  Theoretical study of [ XN5]- (X = O, S, Se, Te) systems.

Authors:  Li Ping Cheng; Xiang Qing Li
Journal:  J Mol Model       Date:  2006-02-25       Impact factor: 1.810

3.  Coordination and Homologation of CO at Al(I): Mechanism and Chain Growth, Branching, Isomerization, and Reduction.

Authors:  Andreas Heilmann; Matthew M D Roy; Agamemnon E Crumpton; Liam P Griffin; Jamie Hicks; Jose M Goicoechea; Simon Aldridge
Journal:  J Am Chem Soc       Date:  2022-07-05       Impact factor: 16.383

  3 in total

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