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Intramolecular Hydrogen Bonding Enhances Stability and Reactivity of Mononuclear Cupric Superoxide Complexes.


ABSTRACT: [(L)CuII(O2•-)]+ (i.e., cupric-superoxo) complexes, as the first and/or key reactive intermediates in (bio)chemical Cu-oxidative processes, including in the monooxygenases PHM and D?M, have been systematically stabilized by intramolecular hydrogen bonding within a TMPA ligand-based framework. Also, gradual strengthening of ligand-derived H-bonding dramatically enhances the [(L)CuII(O2•-)]+ reactivity toward hydrogen-atom abstraction (HAA) of phenolic O-H bonds. Spectroscopic properties of the superoxo complexes and their azido analogues, [(L)CuII(N3-)]+, also systematically change as a function of ligand H-bonding capability.

PROVIDER: S-EPMC6217813 | BioStudies |

REPOSITORIES: biostudies

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