Is NICS a reliable aromaticity index for transition metal clusters?

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• 作者：Cina Foroutan-Nejad
• 关键词：Aromaticity ; Magnetizability ; Current density ; Transition metals ; QTAIM ; NICS
• 刊名：Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
• 出版年：2015
• 出版时间：February 2015
• 年：2015
• 卷：134
• 期：2
• 全文大小：3,937 KB
• 参考文献：1. Bühl M, van Wüllen C (1995) Chem Phys Lett 247:63 CrossRef
  2. Schleyer PvR, Maerker C, Dransfeld A, Jiao H, van Eikema Hommes NJR (1996) J Am Chem Soc 118:6317 CrossRef
  3. Chen Z, Wannere CS, Corminboeuf C, Puchta R, Schleyer PR (2005) Chem Rev 105:3842 CrossRef
  4. Lazzeretti P (2004) Phys Chem Chem Phys 6:217 CrossRef
  5. Feixas F, Matito E, Poater J, Solà M (2008) J Comput Chem 29:1543 CrossRef
  6. Bultinck P (2007) Faraday Discuss 135:347 CrossRef
  7. Jusélius J, Sundholm D (1999) Phys Chem Chem Phys 1:3429 CrossRef
  8. Steiner E, Fowler P, Soncini A, Jenneskens LW (2007) Faraday Discuss 135:309 CrossRef
  9. Jusélius J, Sundholm D (2000) J Org Chem 65:5233 CrossRef
  10. Lin Y-C, Jusélius J, Sundholm D (2005) J Chem Phys 122:214308 CrossRef
  11. Fowler PW, Havenith RWA, Steiner E (2002) Chem Phys Lett 359:530 CrossRef
  12. Jusélius J, Michal S, Sundholm D (2001) J Phys Chem A 105:9939 CrossRef
  13. Lin Y-C, Sundholm D, Jusélius J, Cui L-F, Zhai H-J, Wang L-S (2006) J Phys Chem A 110:4244 CrossRef
  14. Lin Y-C, Sundholm D (2006) J Chem Theory Comput 2:761 CrossRef
  15. Schleyer PR, Freeman P, Jiao H, Goldfuss B (1995) Angew Chem Int Ed 34:337 CrossRef
  16. Cyra?ski MK, Krygowski TM, Katritzky AR, Schleyer PR (2002) J Org Chem 64:1333 CrossRef
  17. Feixas F, Jiménez-Halla JOC, Matito E, Poater J, Solà M (2010) J Chem Theory Comput 6:1118 CrossRef
  18. Badri Z, Pathak S, Fliegl H, Rashidi-Ranjbar P, Bast R, Marek R, Foroutan-Nejad C, Ruud K (2013) J Chem Theory Comput 9:4789 CrossRef
  19. Foroutan-Nejad C, Shahbazian S, Feixas F, Rashidi-Ranjbar P, Solà M (2011) J Comput Chem 32:2422 CrossRef
  20. Badri Z, Foroutan-Nejad C, Rashidi-Ranjbar P (2012) Phys Chem Chem Phys 14:3471 CrossRef
  21. Feixas F, Matito E, Poater J, Solà M (2013) WIREs Comput Mol Sci 3:105 CrossRef
  22. Foroutan-Nejad C, Shahbazian S, Rashidi-Ranjbar P (2010) Phys Chem Chem Phys 12:12630 CrossRef
  23. Foroutan-Nejad C, Badri Z, Shahbazian S, Rashidi-Ranjbar P (2011) J Phys Chem A 115:12708 CrossRef
  24. Stanger A (2006) J Org Chem 71:883 CrossRef
  25. Jiménez-Halla JOC, Matito E, Robles J, Solà M (2006) J Organomet Chem 691:4359
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Theoretical and Computational Chemistry
  Inorganic Chemistry
  Organic Chemistry
  Physical Chemistry
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1432-2234

文摘

In the present account the nature of aromaticity/antiaromaticity of fourteen metallic complexes/clusters are reexamined. These species were classified as aromatic by means of different nucleus independent chemical shift (NICS) based approaches, previously. Visualization of the current density and magnetizability of atomic basins reveals that none of the studied systems are magnetic aromatic, i.e. sustain diamagnetic ring current. It is demonstrated that negative NICS values near the ring plane of the studied molecules originates from remarkably strong local paramagnetic current around their transition metal atom nuclei. This phenomenon has been observed only for Sc3 ?/sup> all-metal cluster but current study demonstrates that the influence of the local paramagnetic currents around transition metal atoms on NICS is a general phenomenon that must be carefully considered prior to classification of the metallic systems as aromatic. Furthermore, this study suggests that NICS is not a reliable aromaticity index for transition-metal clusters/molecules.