title: Addition of dioxygen to an N4S(thiolate) iron(II) cysteine dioxygenase model gives a structurally characterized sulfinato-iron(II) complex.
abstract: The non-heme iron enzyme cysteine dioxygenase (CDO) catalyzes the S-oxygenation of cysteine by O(2) to give cysteine sulfinic acid. The synthesis of a new structural and functional model of the cysteine-bound CDO active site, [Fe(II)(N3PyS)(CH(3)CN)]BF(4) (1) is reported. This complex was prepared with a new facially chelating 4N/1S(thiolate) pentadentate ligand. The reaction of 1 with O(2) resulted in oxygenation of the thiolate donor to afford the doubly oxygenated sulfinate product [Fe(II)(N3PySO(2))(NCS)] (2), which was crystallographically characterized. The thiolate donor provided by the new N3PyS ligand has a dramatic influence on the redox potential and O(2) reactivity of this Fe(II) model complex.
authors.affiliation: Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors.forename: Alison C
authors.initials: AC
authors.lastname: McQuilken
authors.forename: Yunbo
authors.initials: Y
authors.lastname: Jiang
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.forename: David P
authors.initials: DP
authors.lastname: Goldberg
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D020134:Catalytic Domain; D050558:Cysteine Dioxygenase / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013452:Sulfonium Compounds / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D013452:Sulfonium Compounds; D007501:Iron; D050558:Cysteine Dioxygenase; D010100:Oxygen