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Theoretical Chemistry Accounts

, Volume 107, Issue 6, pp 351–356 | Cite as

Ab initio structure and vibrational frequencies of lithium aromatic sulfonyl imide salts

  • S. P. Gejji
  • P. R. Agrawal
  • N. R. Dhumal
Regular article

Abstract.

The structure and vibrational frequencies of an aromatic lithium sulfonyl imide, i.e., lithium bis(4-nitrophenylsulfonyl)imide (LiNPSI) has been studied using self-consistent ab initio Hartree–Fock and hybrid density functional methods. These calculations engender two linkage isomers, which correspond to the local minima on the potential-energy surface. In the lowest-energy isomer, the ligand binds to the metal ion through two oxygens, one from each of the different SO2 groups on the central nitrogen and forms a six-membered ring. Another LiNPSI isomer, wherein the anion coordinates through oxygen and nitrogen atoms and which is 55.9 kJmol−1 higher in energy, has also been obtained. The S–N–S bond angle in the free anion as well as in the LiNPSI complex turns out to be nearly 121°. A comparison of the vibrational spectra of the free NPSI anion and that of the LiNPSI complex reveals that the SO2 stretching vibrations at 1,239 and 1,205 cm−1 can be used to differentiate between the two linkage isomers of the complex. The stronger complexation ability of the NPSI anion, compared to that for (CF3SO2)2N has been explained in terms of the charge density within the molecular electrostatic potential isosurface encompassing both SO2 groups of the anion.

Key words: Molecular electrostatic potential – Hartree–Fock – Hybrid density functional methods 

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Copyright information

© Springer-Verlag Berlin Heidelberg 2002

Authors and Affiliations

  • S. P. Gejji
    • 1
  • P. R. Agrawal
    • 1
  • N. R. Dhumal
    • 1
  1. 1.Department of Chemistry, University of Pune, Pune 411 007, IndiaIN

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