Theoretical study on dissociation of Grignard reagents with several substituents in THF

DOI
  • Kokita Yohei
    Graduate School of Science and Engineering, Yamaguchi University
  • Sumimoto Michinori
    Graduate School of Science and Engineering, Yamaguchi University
  • Yoshimoto Nobuko
    Graduate School of Science and Engineering, Yamaguchi University
  • Hori Kenji
    Graduate School of Science and Engineering, Yamaguchi University

Bibliographic Information

Other Title
  • THF溶媒中の異なる置換基を有するグリニャール試薬の電離に関する理論的研究

Abstract

Magnesium has interesting properties suitable for acting negative electrodes in rechargeable battery. The electrodeposition from THF solution with Grignard reagent is one of the potential methods to make good electrodes. In this study, dissociation of Grignard reagents in solution was analysed using values from quantum mechanical (QM) calculations. Geometry optimizations were performed for Grignard reagents with several substituents, such as methyl, ethyl n-propyl, n-pentyl, n-octyl, and phenyl groups. As we observed ionic conductivities of these reagents dissolved in THF, a PLS regression was applied in order to explain the observed property on the basis of calculated values such as dissociation energies of Mg-Br and Mg-C bonds and their distances, molecular volumes, maximum radius of molecules, r(max), and orbital energies of HOMO and LUMO as explanatory variables. The GA-PLS analysis selected r(max) and LUMO energies as explanatory variables for the PLS regression. The correlation equation from the PLS analysis was used to analyse the mechanism of magnesium deposition in THF with Grignard solution.

Journal

Keywords

Details 詳細情報について

  • CRID
    1390282680714326528
  • NII Article ID
    130004730426
  • DOI
    10.11545/ciqs.2013.0.p10.0
  • Text Lang
    ja
  • Data Source
    • JaLC
    • CiNii Articles
  • Abstract License Flag
    Disallowed

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