Herein, we report a [NiRu] biomimetic system for O 2-tolerant [NiFe]hydrogenases and demonstrate that electron donation to the [NiRu] center can switch the system between the activation of H 2 and O 2 through simple ligand effects by using hexamethylbenzene and pentamethylcyclopentadienyl ligands, respectively. Furthermore, we present the synthesis and direct observations of a [NiRu]-peroxo species, which was formed by the oxygenation of a Ni-SIa model [NiRu] complex, that we propose as a biomimetic analogue of O 2-bound species (OBS) of O 2-tolerant [NiFe]hydrogenases. The [NiRu]-peroxo complex was fully characterized by X-ray analysis, X-ray photoelectron spectroscopy (XPS), mass spectrometry, and 1H NMR spectroscopy. The OBS analogue was capable of oxidizing p-hydroquinone and sodium borohydride to turn back into the Ni-SIa model complex. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
CITATION STYLE
Kim, K., Matsumoto, T., Robertson, A., Nakai, H., & Ogo, S. (2012). Simple ligand effects switch a hydrogenase mimic between H 2 and O 2 activation. Chemistry - An Asian Journal, 7(6), 1394–1400. https://doi.org/10.1002/asia.201101020
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