The ortho C–H bond activation of several pyridine and pyridine N-oxide derivatives mediated by Cp2An(IV)(CH3)2 and Cp2An(III)(CH3) (Cp = C5H5 and An = U, Np, Pu) have been investigated at the DFT level. For uranium(IV) complex, an excellent agreement with experimental observations is found, and particularly in the case of 2-picoline where only ortho sp2 C–H activation is observed without any sp3 C–H activation. These differences of reactivity can be explained by the charges distribution at the metathesis transition state level. A predictive study of the reactivity of neptunium and plutonium complexes with pyridine and pyridine N-oxide is reported. This study shows that neptunium and plutonium have almost the same reactivity. The C–H activation mediated by actinide (III) complexes have found to be more kinetically and thermodynamically favorable than for actinide (IV) complexes. The influence of 5f electrons on organoactinide reactivity is found to be small by comparing implicit and explicit treatment of 5f electrons.
