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Theoretical Study of σ-Bond Activation Reactions and Catalytic Reactions by Transition Metal Complexes

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Practical Aspects of Computational Chemistry II

Abstract

This chapter reports mini-review of theoretical and computational studies of σ-bond activation reactions by transition metal complexes. Because the σ-bond activation reaction through oxidative addition has been theoretically investigated well for long, I wish to focus on the different types of σ-bond activation reactions here. One good example is the C–H σ-bond activation of benzene and methane by Pd(II)–formate complex. The σ-bond activation of methane by Ti(IV)-imido complex is another good example. Their theoretical and computational studies clearly indicate that these reactions are typical heterolytic σ-bond activation without any change of metal oxidation state. The orbital interaction diagram is completely different between the heterolytic σ-bond activation and the oxidative addition reactions; in the heterolytic σ-bond cleavage, the mixing of the C–H σ-bonding orbital into the bonding overlap between the C–H σ*-antibonding and the M–X bonding orbitals plays crucial roles. Theoretical study of oxidative addition to the M–L moiety, which is a new type of σ-bond activation, is also discussed based on theoretical study and recent experimental report. In this reaction, not only metal center but also organic ligand participates in the σ-bond activation reaction like the heterolytic σ-bond activation. However, the metal oxidation state increases by 2 in a formal sense like the usual oxidative addition, which is different from the heterolytic σ-bond activation. The heterolytic σ-bond activation is involved in many catalytic reactions. One of such good examples is Ru-catalyzed hydrogenation of CO2 to formic acid, in which the H–H bond cleavage with the Ru-(η1-OCOH) moiety is involved as a key step. This reaction is essentially the same as the C–H σ-bond activation of benzene with the Pd-(η1-OCOH) moiety. Another example is Pd-catalyzed cross-coupling reaction in which transmetallation is involved as a key step. This transmetallation is understood to be the heterolytic σ-bond activation. I wish to discuss how to accelerate this reaction based on theoretical and computational studies. Recently reported direct-cross coupling reaction occurs via heterolytic C–H σ-bond activation reaction, which is also discussed based on theoretical study.

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Acknowledgements

Many works discussed here were carried out under financial support from Ministry of Education, Culture, Sports, Science, and Technology through Grant-in-Aids of Special Research Field (No. 461; Molecular Theory for Real Systems) and Specially Promoted Research (No.22000009).

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  1. Fukui Institute for Fundamental Chemistry, Kyoto University, Nishihiraki-cho, Takano, Sakyo-ku, Kyoto, 606-8103, Japan

    Shigeyoshi Sakaki

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  1. Jackson State University, P.O. Box 17910, 1400 Lynch St., Jackson, 39217, Mississippi, USA

    Jerzy Leszczynski

  2. Dept. Chemistry, Jackson State University, J. R. Lynch St. 1325, Jackson, 39217, Mississippi, USA

    Manoj K. Shukla

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Sakaki, S. (2012). Theoretical Study of σ-Bond Activation Reactions and Catalytic Reactions by Transition Metal Complexes. In: Leszczynski, J., Shukla, M. (eds) Practical Aspects of Computational Chemistry II. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-0923-2_11

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