Structural Chemistry

, Volume 25, Issue 1, pp 371–376 | Cite as

Theoretical study of geometry and nucleophilicity of the exocyclic methylene in five-membered ring cyclic ketene acetals, neutral and protonated, containing pnictogen and chalcogen heteroatoms

Original Research
First Online:
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Accepted:

Abstract

A series of neutral and protonated five-membered ring cyclic ketene acetals have been examined computationally for any trends in nucleophilicity in the exocyclic methylene and for their ground state geometries. A total of 58 different species were examined, 29 neutral molecules and the corresponding 29 protonated species. The heteroatoms that were used in the heterocyclic ring were a combination of nitrogen, phosphorus, and arsenic from the pnictogen family and oxygen, sulfur, and selenium from the chalcogen family. All geometries were initially optimized at using density functional theory and all stationary points were confirmed to be either minima or transition states through vibrational analysis. All the geometries were consequentially optimized using Møller–Plesset second order perturbation theory with a polarized triple zeta basis set. The main focus of the study was the nucleophilicity of the exocyclic methylene carbon atom and its dependence on heteroatom substitution. As probes for nucleophilicity, the proton affinities of the neutral species, the bond lengths of the exocyclic double bond, and atomic charges were used. The study also resulted in some interesting molecular geometries.

Keywords

MP2 Proton affinities Nucleophilicity Cyclic ketene acetals 
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Notes

Acknowledgments

Funding for this project was provided by NSF EPSCoR #0903787. The authors are also indebted to Dr. Charles Pittman at Mississippi State University for inspiring this study and helpful discussions.

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Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • Adam E. Catoire
    • 1
  • Debbie J. Beard
    • 1
  • Svein Saebo
    • 1
  1. 1.Department of ChemistryMississippi State UniversityMississippi StateUSA

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