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We have used electronic energies here to examine the reaction pathways. The quantitative results and the trends between Th and U would have been equally well given by the enthalpies at 298 K (see Tables S5 and S6 in the Supporting Information, The Gibbs free energies at 298 K also give consistent predictions as given above with the exception of the relative ordering of the Th sp 2 and sp3 activation barriers, 1.4 kcal/mol) compared to ZPE corrected energies, 0.7 kcal/mol) The quantities in context use electronic energies without zero-point corrections. Because the low rotation mode of the methyl group on the picoline ring is constrained in the sp3 activation path, the frequencies of TS5A-2A(sp3) are higher than that of TS5A-1A(sp2, As a result, the lower entropy contribution of TS5A-2A(sp3) leads to a higher Gibbs free energy (G, H, TS) compared to TS5A-1ASP
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