Nucleus-independent chemical shifts (NICS): Distance dependence and revised criteria for aromaticity and antiaromaticity

Journal of Organic Chemistry

Volumn 71, Issue 3, 2006, Pages 883-893

  Stanger, Amnon ^a  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRIC CURRENTS; ELECTRONS; IONS; PARAMAGNETIC MATERIALS; SCANNING;

INTERMEDIATES; NUCLEUS-INDEPENDENT CHEMICAL SHIFTS (NICS); PARAMAGNETIC RING; TRIPLET ELECTRONIC STATES;

AROMATIC COMPOUNDS;

POLYCYCLIC HYDROCARBON;

AROMATIZATION; ARTICLE; CHEMICAL BOND; COMPARATIVE STUDY; ELECTRON; TECHNIQUE;

EID: 32144434172     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo051746o     Document Type: Article

References (40)

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24. VB calculations: Shaik, S.; Shurki, A. Unpublished results.
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26. Both in-plain and out-of-plane components of the isotropic chemical shift contain σ and π contributions. However, the out-of-plane components consists of ca. two-thirds or more of the π contribution. Thus, it is safe to conclude that the out-of-plane component is mainly governed by the π system of the molecule.
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32. The probes are ghost atoms that are called bq's in the Gaussian program. This term will be used throughout this article.
33. The NICS-scan for benzene was calculated at the following levels, using a GIAO procedure: HF: 6-31G, 6-31G*, 6-311G*, 6-311G**, 6-311+G*; B3LYP; 6-311G*, 6-311G**; MP2-6-311G*, 6-311G**. The level used throughout the article was found to be the minimal satisfactory level.
34. Calculated is the planar s-cis-1,3-butadiene with one negative frequency.
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36. Stanger, A. Chem.-Eur. J., in press.
37. This case is similar to that of anthracene. Thus, it is a single π system; therefore, the chemical shifts at different locations above the system cannot be quantitatively compared. The fact that the NICS above the four-membered ring is more negative than that above the six-membered ring actually supports the [10]-annulene structure for 1a.
38. Planar all cis-[10]-annulene has two negative frequencies associated with out-of-plane vibrations.
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40. 6h hexasilabenzene, although NICS(1.0) for both are very similar. The NICS-scan explains this.