A High-Valent Non-Heme ?-Oxo Manganese(IV) Dimer Generated from a Thiolate-Bound Manganese(II) Complex and Dioxygen.

ABSTRACT: This study deals with the unprecedented reactivity of dinuclear non-heme MnII -thiolate complexes with O2 , which dependent on the protonation state of the initial MnII dimer selectively generates either a di-?-oxo or ?-oxo-?-hydroxo MnIV complex. Both dimers have been characterized by different techniques including single-crystal X-ray diffraction and mass spectrometry. Oxygenation reactions carried out with labeled 18 O2 unambiguously show that the oxygen atoms present in the MnIV dimers originate from O2 . Based on experimental observations and DFT calculations, evidence is provided that these MnIV species comproportionate with a MnII precursor to yield ?-oxo and/or ?-hydroxo MnIII dimers. Our work highlights the delicate balance of reaction conditions to control the synthesis of non-heme high-valent ?-oxo and ?-hydroxo Mn species from MnII precursors and O2 .

SUBMITTER: Brazzolotto D 

PROVIDER: S-EPMC5531755 | biostudies-literature | 2017 Jul

REPOSITORIES: biostudies-literature