Spin Polarization Reveals the Coordination Geometry of the [FeFe] Hydrogenase 
Active Site in Its CO-Inhibited State

Reijerse, Eduard J.; Birrell, James A.; Lubitz, Wolfgang

doi:10.1021/acs.jpclett.0c01352

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Spin Polarization Reveals the Coordination Geometry of the [FeFe] Hydrogenase Active Site in Its CO-Inhibited State

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Reijerse, Eduard J.
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Birrell, James A.
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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引用

Reijerse, E. J., Birrell, J. A., & Lubitz, W. (2020). Spin Polarization Reveals the Coordination Geometry of the [FeFe] Hydrogenase Active Site in Its CO-Inhibited State. The Journal of Physical Chemistry Letters, 11(12), 4597-4602. doi:10.1021/acs.jpclett.0c01352.

引用: https://hdl.handle.net/21.11116/0000-0007-D362-C

要旨

The active site of [FeFe] hydrogenase features a binuclear iron cofactor Fe(2)ADT(CO)(3)(CN)(2), where ADT represents the bridging ligand aza-propane-dithiolate. The terminal diatomic ligands all coordinate in a basal configuration, and one CO bridges the two irons leaving an open coordination site at which the hydrogen species and the competitive inhibitor CO bind. Externally supplied CO is expected to coordinate in an apical configuration. However, an alternative configuration has been proposed in which, due to ligand rotation, the CN- bound to the distal Fe becomes apical. Using selective C-13 isotope labeling of the CN- and COext ligands in combination with pulsed C-13 electron-nuclear-nuclear triple resonance spectroscopy, spin polarization effects are revealed that, according to density functional theory calculations, are consistent with only the "unrotated" apical COext configuration.