TY  - JOUR
AU  - Caserta, Giorgio
AU  - Laun, Konstantin
AU  - Oudsen, Jean-Pierre
AU  - Sergueev, Ilya
AU  - Zebger, Ingo
AU  - Lenz, Oliver
TI  - NRVS Spectroscopy Resolves Distinct Bridging Hydride Intermediates in [NiFe]-Hydrogenase
JO  - Journal of the American Chemical Society
VL  - 147
IS  - 45
SN  - 0002-7863
CY  - Washington, DC
PB  - ACS Publications
M1  - PUBDB-2025-04676
SP  - 41216 - 41220
PY  - 2025
N1  - Open Access
AB  - The active-site iron of an H2-sensing [NiFe]-hydrogenase was selectively labeled with 57Fe, allowing the probing of all catalytic intermediates using synchrotron-based nuclear resonance vibrational spectroscopy. Diagnostic metal–hydride vibrations were detected for both the Nia-C and Nia-SR intermediates, with their assignments being confirmed through H/D isotope substitution and in situ hydride photolysis experiments. Interestingly, these Fe–hydride bands are separated by a large energy gap, reflecting distinct bonding interactions at the metal–hydride site. Despite these differences, vibrational analyses across all catalytically active species reveal a conserved structural rigidity of the [NiFe] center, which appears crucial for sustaining efficient and rapid electron transfer in [NiFe]-hydrogenases.
LB  - PUB:(DE-HGF)16
DO  - DOI:10.1021/jacs.5c15408
UR  - https://bib-pubdb1.desy.de/record/639802
ER  -