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A fifteen year contribution of computational studies carried out in close synergy with experiments is summarized. This interplay has allowed some important breakthroughs in the field of organolanthanide chemistry. The variety of different reaction mechanisms in lanthanide chemistry appear to be broader than the simple bond metathesis. [ABSTRACT FROM AUTHOR]

The orthoC–H bond activation of several pyridine and pyridine N-oxide derivatives mediated by Cp2An(iv)(CH3)2and Cp2An(iii)(CH3) (Cp = C5H5and 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 orthosp2C–H activation is observed without any sp3C–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. [ABSTRACT FROM AUTHOR]

Review: [a fifteen year contribution of computation studies in close synergy with experiments; 262 refs. [ABSTRACT FROM AUTHOR]