| Autor: |
Drena A; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States., Fraker A; Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, United States., Thompson NB; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., Doan PE; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States., Hoffman BM; Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States., McSkimming A; Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, United States. |
| Abstrakt: |
The iron-molybdenum cofactor of nitrogenase (FeMoco) catalyzes fixation of N 2 via Fe hydride intermediates. Our understanding of these species has relied heavily on the characterization of well-defined 3d metal hydride complexes, which serve as putative spectroscopic models. Although the Fe ions in FeMoco, a weak-field cluster, are expected to adopt locally high-spin Fe 2+/3+ configurations, synthetically accessible hydride complexes featuring d 5 or d 6 electron counts are almost exclusively low-spin. We report herein the isolation of a terminal hydride complex of four-coordinate, high-spin (d 5 ; S = 5/2) Mn 2+ . Electron paramagnetic resonance and electron-nuclear double resonance studies reveal an unusually large degree of spin density on the hydrido ligand. In light of the isoelectronic relationship between Mn 2+ and Fe 3+ , our results are expected to inform our understanding of the valence electronic structures of reactive hydride intermediates derived from FeMoco. |
