1.
Angew Chem Int Ed Engl
; 56(8): 2208-2211, 2017 02 13.
Artículo
en Inglés
| MEDLINE
| ID: mdl-28079958
RESUMEN
To understand the molecular details of O2 -tolerant hydrogen cycling by a soluble NAD+ -reducing [NiFe] hydrogenase, we herein present the first bioinspired heterobimetallic S-oxygenated [NiFe] complex as a structural and vibrational spectroscopic model for the oxygen-inhibited [NiFe] active site. This compound and its non-S-oxygenated congener were fully characterized, and their electronic structures were elucidated in a combined experimental and theoretical study with emphasis on the bridging sulfenato moiety. Based on the vibrational spectroscopic properties of these complexes, we also propose novel strategies for exploring S-oxygenated intermediates in hydrogenases and similar enzymes.