title: Structural and electronic characterization of non-heme Fe(II)-nitrosyls as biomimetic models of the Fe(B) center of bacterial nitric oxide reductase.
abstract: The detoxification of nitric oxide (NO) by bacterial NO reductase (NorBC) has gained much attention as this reaction provides a paradigm as to how NO can be detoxified anaerobically in cells. However, a clear mechanistic picture of how the heme/non-heme active site of NorBC activates NO is lacking, mostly as a result of insufficient knowledge about the properties of the non-heme iron(II)-NO adduct. Here we report the first biomimetic model complexes for this species that closely resemble the coordination environment found in the protein, using the ligands BMPA-Pr and TPA. The systematic investigation of these compounds allowed us to gain key insight into the electronic structure and geometric properties of high-spin non-heme iron(II)-NO adducts. In particular, we show how small changes in the ligand environment of iron could be used by NorBC to greatly modulate the properties, and hence, the reactivity of this species.
authors.affiliation: Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, USA.
authors.forename: Timothy C
authors.initials: TC
authors.lastname: Berto
authors.forename: Melissa B
authors.initials: MB
authors.lastname: Hoffman
authors.forename: Yuki
authors.initials: Y
authors.lastname: Murata
authors.forename: Kira B
authors.initials: KB
authors.lastname: Landenberger
authors.forename: E Ercan
authors.initials: EE
authors.lastname: Alp
authors.forename: Jiyong
authors.initials: J
authors.lastname: Zhao
authors.forename: Nicolai
authors.initials: N
authors.lastname: Lehnert
mesh_terms: D001419:Bacteria / Q000378:metabolism; D018360:Crystallography, X-Ray; D004583:Electrons; D005296:Ferrous Compounds / Q000737:chemistry*; D008954:Models, Biological; D009569:Nitric Oxide / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010088:Oxidoreductases / Q000737:chemistry*
chemical_list: D005296:Ferrous Compounds; D009942:Organometallic Compounds; D009569:Nitric Oxide; D010088:Oxidoreductases; C034747:nitric-oxide reductase