1 research outputs found
Resonance Raman Spectroscopy on [NiFe] Hydrogenase Provides Structural Insights into Catalytic Intermediates and Reactions
[NiFe] hydrogenases catalyze the
reversible cleavage of hydrogen
and, thus, represent model systems for the investigation and exploitation
of emission-free energy conversion processes. Valuable information
on the underlying molecular mechanisms can be obtained by spectroscopic
techniques that monitor individual catalytic intermediates. Here,
we employed resonance Raman spectroscopy and extended it to the entire
binuclear active site of an oxygen-tolerant [NiFe] hydrogenase by
probing the metal–ligand modes of both the Fe and, for the
first time, the Ni ion. Supported by theoretical methods, this approach
allowed for monitoring H-transfer from the active site and revealed
novel insights into the so far unknown structure and electronic configuration
of the hydrogen-binding intermediate of the catalytic cycle, thereby
providing key information about catalytic intermediates and reactions
of biological hydrogen activation