A theoretical study of the oxidative addition of C - C vs C - H bonds to a rhodium(I) complex with PCP-type ligands has been carried out. Special attention has been paid to the effect of different bulky substituents at the phosphorus atoms of the chelate ligand. Therefore, B3LYP/lanl2dz+p//B3LYP/lanl2dz and ONIOM(B3LYP/lanl2dz+p:B3LYP/lanl2dz)//ONIOM(B3LYP/lanl2dz:HF/lanl 1mb) methods have been utilized. According to the calculations, C - H activation is always the kinetically favored process (ΔΔE(≠) 20 kJ·mol-1), though the C - C activation product is more stable (ΔΔE 20 kJ·mol-1). C - H addition is a reversible process; the product of the C - H activation can interconvert to the C - C activation product via an intermediate structure. Bulky substituents are found to increase the barrier for C-H activation relative to that for C - C activation. With additional ligands (e.g., phosphines), hexacoordinate complexes are formed. This is more favorable for the C - C activation products. Our calculations show that the activation reaction proceeds via complexes with a pentacoordinated rhodium atom. Thus, in the presence of donor ligands, the activation reaction is inhibited.
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