title: Model study of CO inhibition of [NiFe]hydrogenase.
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.
authors.affiliation: Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
authors.forename: Takahiro
authors.initials: T
authors.lastname: Matsumoto
authors.forename: Ryota
authors.initials: R
authors.lastname: Kabe
authors.forename: Kyoshiro
authors.initials: K
authors.lastname: Nonaka
authors.forename: Tatsuya
authors.initials: T
authors.lastname: Ando
authors.forename: Ki-Seok
authors.initials: KS
authors.lastname: Yoon
authors.forename: Hidetaka
authors.initials: H
authors.lastname: Nakai
authors.forename: Seiji
authors.initials: S
authors.lastname: Ogo
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry / Q000378:metabolism*; D002248:Carbon Monoxide / Q000378:metabolism*; D006864:Hydrogenase / Q000037:antagonists & inhibitors* / Q000378:metabolism*; D008954:Models, Biological; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry / Q000378:metabolism*; D017975:Ruthenium Compounds / Q000737:chemistry / Q000378:metabolism*
chemical_list: D017975:Ruthenium Compounds; D009532:Nickel; D002248:Carbon Monoxide; C043296:nickel-iron hydrogenase; D006864:Hydrogenase