title: How do the thiolate ligand and its relative position control the oxygen activation in the cysteine dioxygenase model?
abstract: In the iron(II)-thiolate models of cysteine dioxygenase, the thiolate ligand is a key factor in the oxygen activation. In this contribution, four model compounds have been theoretically investigated. This comparative study reveals that the thiolate ligand itself and its relative position are both important for the activation of O(2). Before the O(2) binding, the thiolate ligand must transfer charge to Fe(II), and the effective nuclear charges of Fe(II) is decreased, which results in a lower redox potential of compounds. In other words, the thiolate ligand provides a prerequisite for the O(2) activation. Furthermore, the relative position of the thiolate ligand is discovered to determine the reaction path of O(2) activation. The amount of charge transfer is crucial for these reactions; the more charge it transfers, the lower the related redox potentials. This work really helps think deeper into the O(2) activation process of mononuclear nonheme iron enzymes.
authors.affiliation: Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, Institute of Theoretical Chemistry, School of Chemistry & Chemical Engineering, Shandong University, Jinan 250100, P. R. China.
authors.forename: Xin
authors.initials: X
authors.lastname: Che
authors.forename: Jun
authors.initials: J
authors.lastname: Gao
authors.forename: Dongju
authors.initials: D
authors.lastname: Zhang
authors.forename: Chengbu
authors.initials: C
authors.lastname: Liu
mesh_terms: D003198:Computer Simulation; D056831:Coordination Complexes / Q000737:chemistry*; D050558:Cysteine Dioxygenase / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D005296:Ferrous Compounds; D008024:Ligands; D013438:Sulfhydryl Compounds; D050558:Cysteine Dioxygenase; D010100:Oxygen