A Nonheme Thiolate-Ligated Cobalt Superoxo Complex: Synthesis and Spectroscopic Characterization, Computational Studies, and Hydrogen Atom Abstraction Reactivity.

ABSTRACT: The synthesis and characterization of a Co(II) dithiolato complex Co(Me₃TACN)(S₂SiMe₂) (1) are reported. Reaction of 1 with O₂ generates a rare thiolate-ligated cobalt-superoxo species Co(O₂)(Me₃TACN)(S₂SiMe₂) (2) that was characterized spectroscopically and structurally by resonance Raman, EPR, and X-ray absorption spectroscopies as well as density functional theory. Metal-superoxo species are proposed to S-oxygenate metal-bound thiolate donors in nonheme thiol dioxygenases, but 2 does not lead to S-oxygenation of the intramolecular thiolate donors and does not react with exogenous sulfur donors. However, complex 2 is capable of oxidizing the O-H bonds of 2,2,6,6-tetramethylpiperidin-1-ol derivatives v

SUBMITTER: Gordon JB 

PROVIDER: S-EPMC6556537 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature