Simple Ligand Effects Switch a Hydrogenase Mimic between H2 and O2 Activation |
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| Authors: | Kyoungmok Kim Dr. Takahiro Matsumoto Dr. Andrew Robertson Dr. Hidetaka Nakai Prof. Seiji Ogo |
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| Affiliation: | 1. Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto‐oka, Nishi‐ku, Fukuoka 819‐0395 (Japan), Fax: (+81)?92‐802‐2823;2. International Institute for Carbon‐Neutral Energy Research (WPI‐I2CNER), Kyushu University, 744 Moto‐oka, Nishi‐ku, Fukuoka 819‐0395 (Japan);3. International Education Center, Kyushu University, 744 Moto‐oka, Nishi‐ku, Fukuoka 819‐0395 (Japan);4. Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), Kawaguchi Center Building, 4‐1‐8 Honcho, Kawaguchi‐shi, Saitama 332‐0012 (Japan) |
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| Abstract: | Herein, we report a [NiRu] biomimetic system for O2‐tolerant [NiFe]hydrogenases and demonstrate that electron donation to the [NiRu] center can switch the system between the activation of H2 and O2 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 O2‐bound species (OBS) of O2‐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. |
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| Keywords: | bioinorganic chemistry biomimetic compounds hydrogen ligand effects oxygen |
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