Structures and Proton Transfer for Malonaldehyde Cyclamers II Nonplanar Structures

DOI

Bibliographic Information

Other Title
  • マロンアルデヒド環状体の構造と水素移動 II 非平面構造

Abstract

In order to elucidate the possibility of hydrogen transfer in the cyclic conjugated hydrogen-bonding system of malonaldehyde enols (the n-meric cyclamers of malonaldehyde, CMAn with n=3-10) DFT calculations were performed using B3LYP functionals with the 6-31G** basis sets. Two stable geometries with forms I and II about the hydrogen bonds in the cyclamers are defined as "[syn-anti]anti" and "[anti-syn]anti," respectively, on the basis of the CC-OH and CC=O...H configurations and the CO...OC conformation. Planar stable structures were obtained only for form I of CMA5 and CMA6. Bowl, chair, boat, and crown structures were found as nonplanar stable ones for the rest forms of CMA3-8. The energy differences between the two forms are very small for the chair and boat structures of CMA8. The barrier heights for the proton transfer are also very small for both the forms of CMA8. The values for the barrier heights reduce to 0.3-4 kcal/mol with the zero-point energy correction. The proton transfer for CMAn should exist for the chair and boat structures of CMA8 even in the solid state.

Journal

Keywords

Details 詳細情報について

  • CRID
    1390282680713928960
  • NII Article ID
    130004575210
  • DOI
    10.11545/ciqs.tokyo.0.jp04.0
  • Data Source
    • JaLC
    • CiNii Articles
  • Abstract License Flag
    Disallowed

Report a problem

Back to top