Upon deprotonation of the tBuPNNP ligand going from 3 to 4, the valence electronic structure changes significantly. A decrease in the transition to the Co 3𝑑 𝑧 2 level by ~0.3 eV is evident in the HERFD-XAS data and reproduced by the computed spectra. As described above, the Co 3𝑑 𝑧 2 level is destabilized by σ-overlap with the terminal H 1s and N 2p orbitals. DFToptimized structures show a 0.04 Å increase in Co-N distance going from 3 to 4, with minimal change in Co distance to the terminal H ligands (Table ). This geometric change is present for both Co-N bonds and is not localized near the site of deprotonation. The increase in Co-N bond length from 3 to 4 decreases orbital overlap of N 2p with Co 3𝑑 𝑧 2 , resulting in less destabilization and a lower Co K-pre-edge transition energy. Hirshfeld charges show no significant difference in electron density on Co between 3 and 4 (Table ). Thus, although deprotonation of the tBuPNNP ligand does not strongly affect the charge density on Co, the metal electronic structure is significantly impacted via geometric differences in coordination with the ligands.