Metal-Assisted Oxo Atom Addition to an Fe(III) Thiolate.

ABSTRACT: Cysteinate oxygenation is intimately tied to the function of both cysteine dioxygenases (CDOs) and nitrile hydratases (NHases), and yet the mechanisms by which sulfurs are oxidized by these enzymes are unknown, in part because intermediates have yet to be observed. Herein, we report a five-coordinate bis-thiolate ligated Fe(III) complex, [Fe^III(S₂^Me2N₃(Pr,Pr))]⁺ (2), that reacts with oxo atom donors (PhIO, IBX-ester, and H₂O₂) to afford a rare example of a singly oxygenated sulfenate, [Fe^III(η²-S^Me2O)(S^Me2)N₃(Pr,Pr)]⁺ (5), resembling both a proposed intermediate in the CDO catalytic cycle and the essential NHase Fe-S(O)^Cys114 proposed to

SUBMITTER: Villar-Acevedo G 

PROVIDER: S-EPMC5262503 | biostudies-literature | 2017 Jan

REPOSITORIES: biostudies-literature