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Accelerated Oxygen Atom Transfer and C−H Bond Oxygenation by Remote Redox Changes in Fe 3 Mn‐Iodosobenzene Adducts
Author(s) -
de Ruiter Graham,
Carsch Kurtis M.,
Gul Sheraz,
Chatterjee Ruchira,
Thompson Niklas B.,
Takase Michael K.,
Yano Junko,
Agapie Theodor
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201701319
Subject(s) - redox , chemistry , reactivity (psychology) , adduct , oxidation state , electron transfer , metal , oxygen , crystallography , photochemistry , atom (system on chip) , inorganic chemistry , organic chemistry , medicine , alternative medicine , pathology , computer science , embedded system
Abstract We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x ( 3 : x =2; 4 : x =3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X‐ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X‐ray absorption spectroscopy provided unique insights into how changes in oxidation state ( Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one‐electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.