Yu Lan - Computational Methods in Organometallic Catalysis

Scheme 1.6 Mechanism of rhodium‐catalyzed coupling reaction of quinoline N ‐oxide and acetylenes.

Source: From Li et al. [88].

In fact, quantum chemical calculations have become one of the conventional methods to study the mechanism of transition metal catalysis ( Scheme 1.7). The basis function of computational organometallic chemistry is to calculate the geometries and energies of stationary points, including local minimums and transition states, so as to construct potential energy surface for the catalytic cycle and explore the reaction mechanism. Information of molecular orbital, charge distribution, dipole moment, and so on can be achieved by computational population analysis, which is propitious to study factors of reactivity and selectivity. More useful information, including infrared, nuclear magnetic resonance, circular dichroism spectra, dispersion interactions, nucleophilicity/electrophilicity, and aromaticity, also can be achieved by theoretical calculations for organometallic chemistry.

Scheme 1.7 Mechanism study of organometallic catalysis by density functional theory (DFT) calculations.

Over recent several decades, massive experimental and theoretical investigations were reported about organometallic catalysis. In those works, theoretical studies have proved to be indispensable routine technique for modern synthetic organic chemistry. Consequently, we herein provide a book to summarize and generalize the theoretical advances regarding organometallic catalysis. In Chapter 2, we summarize the popular computational methods, which are of benefit for the mechanism study of organometallic catalysis. We discuss the theoretical studies of elementary reactions in Chapter 3. Detailed processes for all the familiar elementary reactions in organometallic catalysis discovered by theoretical calculations are summarized in this chapter. Based on those two chapters, the second part of this book is organized by the type of transition metals, which are used as catalyst in organic reactions.

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