EPR and ³¹P ENDOR Characterization of Pseudo-Jahn-Teller Dynamics and N₂ Activation in Functional Nitrogenase Models, P₃^EM(N₂) (M = Fe, Co; E = Si, B, C).

ABSTRACT: The nominally trigonal, pseudo-Jahn-Teller (PJT)-active, S = 1/2 N₂-bound complexes, P₃^EM(N₂), M = Fe, Co, with three in-plane phosphine ligands and axial donors, E = Si, B, C, include functional nitrogenase models that catalyze the reduction of N₂ to NH₃. We applied EPR, ³¹P ENDOR spectroscopy, and DFT computations to characterize the PJT-induced distortions of four selected P₃^EM(N₂), revealing how the metal ion and axial ligand E together tune both PJT dynamics, as revealed by ³¹P ENDOR and N₂ activation, as indicated by a decrease in N≡N stretching frequency, ν(N≡N).

SUBMITTER: Yang H 

PROVIDER: S-EPMC12927471 | biostudies-literature | 2025 Sep

REPOSITORIES: biostudies-literature