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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

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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.

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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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Authors and Affiliations

  1. Department of Chemistry, Mississippi State University, P.O. Box 9573, Mississippi State, MS, 3975, USA

    Adam E. Catoire, Debbie J. Beard & Svein Saebo

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  1. Adam E. Catoire
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  2. Debbie J. Beard
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  3. Svein Saebo
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Correspondence to Svein Saebo.

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Catoire, A.E., Beard, D.J. & Saebo, S. 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. Struct Chem 25, 371–376 (2014). https://doi.org/10.1007/s11224-013-0338-6

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  • DOI: https://doi.org/10.1007/s11224-013-0338-6

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