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Rh-catalyzed C–H bond functionalization can construct the C–heteroatom bonds by selecting substrates that contain heteroatoms. Despite the dominance of Rh-catalyzed C–C bond formation through C–H activation, Rh-catalyzed C–X (X = N, O, halide, B, Si) bond formation reactions through C–H bond functionalization have also been well developed and studied theoretically in detail recently. In this chapter, the theoretical studies of Rh-catalyzed C–H bond activation and C–O bond, C–N bond, C–halide bond, C–B bond, and C–Si bond formation were discussed. This volume provides valuable insight into the mechanism and the origin of the regio- and stereoselectivity for these Rh-catalyzed C–H bond activation reactions.

The density functional theory (DFT) method is the most popular theoretical treatment for the computational investigation of Rh-catalyzed C–H functionalization. In this chapter, the definition of the DFT method and the classification of functionals based on the “Jacob’s ladder” were introduced. The B3LYP functional was discussed in detail because of its comprehensive performance in Rh-catalyzed C–H functionalization. We further introduced the Minnesota series functional, which is one of the best alternative functionals of B3-LYP. Especially, M06-L and M11-L have good performance for energy calculations in Rh-catalyzed C–H functionalization reaction. The popular basis sets and solvent models were then discussed.

C–C bond formation has attracted enormous research interest and lots of synthesis methods were applied to it in recent years. Accordingly, more and more efforts were put into the theoretical study of Rh-catalyzed C–C bond formation through C–H activation because of the complexity of the C–H bond activation reaction itself and its mechanism. In this chapter, the theoretical studies of Rh-catalyzed C–H bond arylation through electrophiles and nucleophile aryl reagents were first discussed. Subsequently, the mechanisms of C–H bond alkylation by using olefins alkynes and diazo compound along with C–H bond alkenylation by using olefins and alkynes were analyzed from theoretical points of view. The mechanisms of C–H bond alkynylation, C–H bond carbonylation, C–H bond annulation with directing group as electrophile, nucleophile, and internal oxidants were further discussed on account of related contributions. Finally, the mechanisms of the outer-sphere C–H activation, sequential C–H activation, and inner-sphere carbene insertion were theoretically considered to provide a whole picture of the C–C bond formation via C–H activation.