Strong hyperconjugative interactions in isolated and water complexes of desflurane: a theoretical investigation.

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  • Author(s): Sutradhar D;Sutradhar D; Zeegers-Huyskens T; Chandra AK
  • Source:
    The journal of physical chemistry. A [J Phys Chem A] 2013 Sep 12; Vol. 117 (36), pp. 8545-54. Date of Electronic Publication: 2013 Apr 16.
  • Publication Type:
    Journal Article; Research Support, Non-U.S. Gov't
  • Language:
    English
  • Additional Information
    • Source:
      Publisher: American Chemical Society Country of Publication: United States NLM ID: 9890903 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5215 (Electronic) Linking ISSN: 10895639 NLM ISO Abbreviation: J Phys Chem A Subsets: MEDLINE
    • Publication Information:
      Original Publication: Washington, D.C. : American Chemical Society, c1997-
    • Subject Terms:
      Quantum Theory*; Isoflurane/*analogs & derivatives ; Water/*chemistry; Desflurane ; Hydrogen Bonding ; Hydrogen-Ion Concentration ; Isoflurane/chemistry ; Models, Molecular ; Molecular Conformation ; Thermodynamics
    • Abstract:
      Ab initio MP2/aug-cc-pvDZ and density functional B3LYP calculations with the 6-311++G(d,p) basis set are performed to investigate the conformation of desflurane (CHF2OCHFCF3), its acidity/basicity and its interaction with one water molecule. The calculations include the optimized geometries, the harmonic frequencies of relevant vibrational modes, the binding energies with water, and a detailed natural bond orbital (NBO) analysis Iincluding the NBO charges, the hybridization of the C atoms and the intra- and intermolecular hyperconjugations. The relative energies of the two most stable conformers are discussed as a function of the total hyperconjugative energies resulting from the interaction of lone pairs of the O and F atoms to the different antibonding orbitals of desflurane. The proton affinity is the same for both conformers but the acidity of the CH bond is larger for the less stable conformer. The binding energies of the complexes of two desflurane conformers with one water molecule range from -2.75 to -3.23 kcal mol(-1). Depending on the structure of the complexes, the CH bonds involved in the interaction are contracted or elongated. The σ*(CH) occupation predominates over the hybridization effect in determining the CH bond length. There is an unexpected charge transfer to the external OH bond of the water molecule. This effect is in good agreement with theoretical data on the complexes between fluorinated dimethyl ethers and water and seems to depend on the number of F atoms implanted on the ether molecule.
    • Accession Number:
      059QF0KO0R (Water)
      CRS35BZ94Q (Desflurane)
      CYS9AKD70P (Isoflurane)
    • Publication Date:
      Date Created: 20130404 Date Completed: 20140319 Latest Revision: 20181202
    • Publication Date:
      20240829
    • Accession Number:
      10.1021/jp402023u
    • Accession Number:
      23547928