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A New Domain of Reactivity for High-Valent Dinuclear [M(μ-O)2M′] Complexes in Oxidation Reactions
Citation key ANIE:ANIE201607611
Author Engelmann, Xenia and Yao, Shenglai and Farquhar, Erik R. and Szilvási, Tibor and Kuhlmann, Uwe and Hildebrandt, Peter and Driess, Matthias and Ray, Kallol
Pages 297–301
Year 2017
ISSN 1521-3773
DOI 10.1002/anie.201607611
Journal Angewandte Chemie International Edition
Volume 56
Number 1
Abstract The strikingly different reactivity of a series of homo- and heterodinuclear [(MIII)(μ-O)2(MIII)′]2+ (M=Ni; M′=Fe, Co, Ni and M=M′=Co) complexes with β-diketiminate ligands in electrophilic and nucleophilic oxidation reactions is reported, and can be correlated to the spectroscopic features of the [(MIII)(μ-O)2(MIII)′]2+ core. In particular, the unprecedented nucleophilic reactivity of the symmetric [NiIII(μ-O)2NiIII]2+ complex and the decay of the asymmetric [NiIII(μ-O)2CoIII]2+ core through aromatic hydroxylation reactions represent a new domain for high-valent bis(μ-oxido)dimetal reactivity.
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