A theoretical probe of high-valence uranium and transuranium silylamides: Structural and redox properties

A mixed character involving both metal and pyridines has been proposed for the reduction process of AnpyNH via relativistic DFT calculations, but a metal-based reduction mechanism suggested for thf-coordinated complexes. The solvent polarity and equatorial coordination environment play a significant role in calculating the reduction potentials (E0). The marked E0 shift for the thf-coordinated actinyl silylamides is elucidated by the different electron-donating ability of equatorial NSiH3 and NSiMe3 groups.