Model study of CO inhibition of [NiFe]hydrogenase |
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Authors: | Matsumoto Takahiro Kabe Ryota Nonaka Kyoshiro Ando Tatsuya Yoon Ki-Seok Nakai Hidetaka Ogo Seiji |
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Affiliation: | Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan. |
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Abstract: | We propose a modified mechanism for the inhibition of NiFe]hydrogenase (NiFe]H(2)ase) by CO. We present a model study, using a NiRu H(2)ase mimic, that demonstrates that (i) CO completely inhibits the catalytic cycle of the model compound, (ii) CO prefers to coordinate to the Ru(II) center rather than taking an axial position on the Ni(II) center, and (iii) CO is unable to displace a hydrido ligand from the NiRu center. We combine these studies with a reevaluation of previous studies to propose that, under normal circumstances, CO inhibits NiFe]H(2)ase by complexing to the Fe(II) center. |
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