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A Polysiloxide Complex with two Chromium(III) η 2 ‐Superoxo Moieties
Author(s) -
Wind MarieLouise,
BraunCula Beatrice,
Schax Fabian,
Herwig Christian,
Limberg Christian
Publication year - 2020
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.201900119
Subject(s) - chemistry , chromium , reactivity (psychology) , transition metal , stereochemistry , metal , medicinal chemistry , crystallography , photochemistry , catalysis , organic chemistry , medicine , alternative medicine , pathology
Abstract The isolation and identification of intermediates formed in the course of the activation of dioxygen at transition metal centers reveals important mechanistic insights concerning such processes. We previously reported the reaction of the dinuclear Cr II complex [L 2 Cr 2 (MeCN) 2 ][Li(MeCN)] 2 (L=PhSi(OSiPh 2 O − ) 3 ) ( 5 ) with dioxygen, which resulted in the formation of the Cr IV oxo complex [L 2 Cr 2 O 2 ][Li(THF) 2 ] 2 ( 6 ), as the final room temperature stable product. Here we now report the isolation and characterization of an intermediate en route to 6 , namely the dinuclear Cr III superoxo complex [L 2 Cr 2 (O 2 ) 2 ][Li(MeCN)] 2 ( 7 ). 7 is the first example of a structurally characterized dinuclear Cr III superoxo complex with two independent side‐on bound superoxo ligands. Reactivity studies outline the capability of this superoxo complex to activate weak O−H bonds.