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Quantum mechanical study of the alkoxide-independent pathway of reductive elimination of C–O from palladium (p-cyanophenyl) neopentoxide complex

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Abstract

In this study the alkoxide-independent pathway of reductive elimination of C–O from palladium (p-cyanophenyl) neopentoxide complex in THF at 47 °C was investigated theoretically by use of density functional theory and the solvent polarized continuum model. On the basis of experimental results a two-pathway mechanism had been proposed: a concerted process (path a) and a two-step process (path b) initiated by inner-sphere attack of the alkoxide ligand on the ipso-carbon atom of the palladium-bound aryl group (step 1) then Pd–C heterolysis to form p-neopentoxybenzonitrile (step 2). The activation energies of the two pathways were calculated by use of the quantum mechanical approach and compared with each other and with experimental results.

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Acknowledgments

We thank the Center of Theoretical Research of the Kharazmi Institute for allocation of computer time.

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Authors and Affiliations

  1. Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran

    Mehran Najafi Ardabili, Ali Morsali, S. Ali Beyramabadi, Hamed Chegini & Azar Gharib

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  1. Mehran Najafi Ardabili
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  2. Ali Morsali
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  3. S. Ali Beyramabadi
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  4. Hamed Chegini
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  5. Azar Gharib
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Correspondence to Ali Morsali.

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Ardabili, M.N., Morsali, A., Beyramabadi, S.A. et al. Quantum mechanical study of the alkoxide-independent pathway of reductive elimination of C–O from palladium (p-cyanophenyl) neopentoxide complex. Res Chem Intermed 41, 5389–5398 (2015). https://doi.org/10.1007/s11164-014-1640-7

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