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Computational study of the substitution effect on the mechanism for phospha-Wittig reaction

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Abstract

The phospha-Wittig reaction HP=PH3 + O=CHX → HP=CHX + O=PH3 (X = H, F, Cl, Me, OMe, NMe2, CMe3) was examined using the density functional theory calculations. All of the structures were completely optimized at the B3LYP/6-311++G** level of theory. The reactivities of various O=CHX were examined by estimating their activation energies. The main finding of this work is that the configuration mixing model can successfully predict the relative ordering of the activation energy and reaction enthalpies of the phospha-Wittig reaction. It was demonstrated that O=CHX with more electro-releasing substituents will possess a smaller singlet–triplet splitting. This will facilitate the phospha-Wittig reaction and will result in a larger exothermicity.

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Acknowledgments

The author is grateful to the National Center for High-performance Computing for computer time and facilities. The author also thank the National Science Council of Taiwan for financial support (NSC 97-2113-M-152-001-MY2) and Prof. Dr. San-Yan Chu for helpful and generous suggestions. Also, the author acknowledges the referees for their useful comments.

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  1. Department of Science Education, National Taipei University of Education, Taipei, 10659, Taiwan

    Hsin-Yi Liao

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Liao, HY. Computational study of the substitution effect on the mechanism for phospha-Wittig reaction. Theor Chem Acc 124, 49–57 (2009). https://doi.org/10.1007/s00214-009-0579-z

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  • DOI: https://doi.org/10.1007/s00214-009-0579-z

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