Which NICS Method is Most Consistent with Ring Current Analysis? Assessment in Simple Monocycles

Overview

Journal RSC Adv

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 May 11

PMID 35542548

Authors

R Baez-Grez

Lina Ruiz

R Pino-Rios

W Tiznado

Affiliations

Soon will be listed here.

Abstract

The aromaticity of benzene, Al cluster, cyclopropane, borazine and planar cyclooctatetraene (COT) was analyzed according to different strategies based on nucleus-independent chemical shift (NICS) computations. The analysis of NICS-components evolution along the main molecular axis seems to be the most adequate and simplest strategy to predict the aromatic or antiaromatic character of the studied systems. Moreover, the analysis of the σ- and π-electron contributions to the out-of-plane component of NICS (NICS ) leads to the same qualitative and quantitative conclusions previously obtained by the analysis of the magnetically induced ring current densities.

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References

Randic M . Aromaticity of polycyclic conjugated hydrocarbons. Chem Rev. 2003; 103(9):3449-605. DOI: 10.1021/cr9903656. View

Havenith R, Fowler P . The origin of the ring current in the all-metal aromatic, Al(4)(2-). Phys Chem Chem Phys. 2006; 8(29):3383-6. DOI: 10.1039/b607410c. View

Monaco G, Zanasi R, Pelloni S, Lazzeretti P . Relative Weights of σ and π Ring Currents in a Few Simple Monocycles. J Chem Theory Comput. 2015; 6(11):3343-51. DOI: 10.1021/ct100442j. View

Perdew , Chevary , Vosko , Jackson , Pederson , Singh . Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Phys Rev B Condens Matter. 1992; 46(11):6671-6687. DOI: 10.1103/physrevb.46.6671. View

Papadopoulos A, Charistos N, Kyriakidou K, Sigalas M . Study of Electron Delocalization in 1,2-, 1,3-, and 1,4-Azaborines Based on the Canonical Molecular Orbital Contributions to the Induced Magnetic Field and Polyelectron Population Analysis. J Phys Chem A. 2015; 119(39):10091-100. DOI: 10.1021/acs.jpca.5b06027. View

Feixas F, Matito E, Poater J, Sola M . Quantifying aromaticity with electron delocalisation measures. Chem Soc Rev. 2015; 44(18):6434-51. DOI: 10.1039/c5cs00066a. View

Merino G, Heine T, Seifert G . The induced magnetic field in cyclic molecules. Chemistry. 2004; 10(17):4367-71. DOI: 10.1002/chem.200400457. View

Torres J, Islas R, Osorio E, Harrison J, Tiznado W, Merino G . Is Al2Cl6 aromatic? Cautions in superficial NICS interpretation. J Phys Chem A. 2013; 117(26):5529-33. DOI: 10.1021/jp403465f. View

Bultinck P, Fias S, Ponec R . Local aromaticity in polycyclic aromatic hydrocarbons: electron delocalization versus magnetic indices. Chemistry. 2006; 12(34):8813-8. DOI: 10.1002/chem.200600541. View

10.

Charistos N, Papadopoulos A, Sigalas M . Interpretation of electron delocalization in benzene, cyclobutadiene, and borazine based on visualization of individual molecular orbital contributions to the induced magnetic field. J Phys Chem A. 2014; 118(6):1113-22. DOI: 10.1021/jp411410r. View

11.

Stanger A . Nucleus-independent chemical shifts (NICS): distance dependence and revised criteria for aromaticity and antiaromaticity. J Org Chem. 2006; 71(3):883-93. DOI: 10.1021/jo051746o. View

12.

Schleyer P, Maerker C, Dransfeld A, Jiao H, van Eikema Hommes N . Nucleus-Independent Chemical Shifts: A Simple and Efficient Aromaticity Probe. J Am Chem Soc. 2017; 118(26):6317-6318. DOI: 10.1021/ja960582d. View

13.

Heine T, Corminboeuf C, Seifert G . The magnetic shielding function of molecules and pi-electron delocalization. Chem Rev. 2005; 105(10):3889-910. DOI: 10.1021/cr030082k. View

14.

Van Damme S, Acke G, Havenith R, Bultinck P . Can the current density map topology be extracted from the nucleus independent chemical shifts?. Phys Chem Chem Phys. 2016; 18(17):11746-55. DOI: 10.1039/c5cp07170d. View

15.

Lin Y, Juselius J, Sundholm D, Gauss J . Magnetically induced current densities in Al4 (2-) and Al4 (4-) species studied at the coupled-cluster level. J Chem Phys. 2005; 122(21):214308. DOI: 10.1063/1.1924590. View

16.

Fallah-Bagher-Shaidaei H, Wannere C, Corminboeuf C, Puchta R, Schleyer P . Which NICS aromaticity index for planar pi rings is best?. Org Lett. 2006; 8(5):863-6. DOI: 10.1021/ol0529546. View

17.

Gomes J, Mallion R . Aromaticity and ring currents. Chem Rev. 2001; 101(5):1349-83. DOI: 10.1021/cr990323h. View

18.

Carion R, Champagne B, Monaco G, Zanasi R, Pelloni S, Lazzeretti P . Ring Current Model and Anisotropic Magnetic Response of Cyclopropane. J Chem Theory Comput. 2015; 6(7):2002-18. DOI: 10.1021/ct100175j. View

19.

Torres-Vega J, Vasquez-Espinal A, Ruiz L, Fernandez-Herrera M, Alvarez-Thon L, Merino G . Revisiting Aromaticity and Chemical Bonding of Fluorinated Benzene Derivatives. ChemistryOpen. 2015; 4(3):302-7. PMC: 4522180. DOI: 10.1002/open.201402110. View

20.

Holmes S, Bai S, Iuliucci R, Mueller K, Dybowski C . Calculations of solid-state Ca NMR parameters: A comparison of periodic and cluster approaches and an evaluation of DFT functionals. J Comput Chem. 2017; 38(13):949-956. DOI: 10.1002/jcc.24763. View