Abstract
The free energies of reaction and the activation energies are calculated, with DFT (B3PW91) and small RECP (relativistic core potential) for uranium, for the reaction of Cp2UNMe and Cp2UO with MeCtCMe and H3Si-Cl that yields the corresponding addition products. CAS(2,7) and DFT calculations on Cp2UO and Cp2UNMe give similar results, which validates the use of DFT calculations in these cases. The calculated results mirror the experimental reaction of [1,2,4-(CMe3)3C5H2]2UNMe with dimethylacetylene and [1,2,4-(CMe3)3C5H2]2UO with Me3SiCl. The net reactions are controlled by the change in free energy between the products and reactants, not by the activation energies, and therefore by the nature of the UO and UNMe bonds in the initial and final states. A NBO analysis indicates that the U-O interaction in Cp2UO is composed of a single U-O ó bond with three lone pairs of electrons localized on oxygen, leading to a polarized U-O fragment. In contrast, the U-NMe interaction in Cp2- UNMe is composed of a ó and ð component and a lone pair of electrons localized on the nitrogen, resulting in a less polarized UNMe fragment, in accord with the lower electronegativity of NMe relative to O. The strongly polarized U(+)-O(-) bond is calculated to be about 70 kcal mol-1 stronger than the less polarized UdNMe bond.