Two nitrogen-rich, isostructural complexes of uranium and thorium, (C5Me5)(2)U[eta(2)-(N,N')-tetrazolate](2), (7) and (C5Me5)(2)Th[eta(2)-(NnN'-tetrazolate], (8), containing 5methyltetrazolate) have been synthesized and structurally characterized by single-crystal X-ray diffraction, electro-chemical methods, UV-visible near-IR spectroscopy, and variable-temperature H-1 NMR spectroscopy. Density functional theory (DFT) calculations yield favorable free energies of formation (approximately -375 kJ/mol) and optimized structures in good agreement with the experimental crystal structures. Additionally, calculated NMR chemical shifts of 7 and 8 are in good agreement with the variable -temperature H-1 NMR. experiments. Time-dependent DFT calculations of both complexes yield UV visible spectroscopic features that are consistent with experiment and provide assignments of the corresponding electronic transitions. The electronic transitions in the UV visible spectroscopic region are attributed to C5Me5 ligand-to-metal charge transfer. The low-lying molecular orbitals of the tetrazolate ligands (similar to 2 eV below the HOMO) do not contribute appreciably to experimentally observed electronic transitiohsrThe combined experimental and theoretical analysis of these new nitrogen-rich uranium and thorium complexes indicates the tetrazolate ligand 'behaves primarily as a sigma-donor.