Xenia Engelmann1, Shenglai Yao2, Erik R Farquhar3, Tibor Szilvási4, Uwe Kuhlmann2, Peter Hildebrandt2, Matthias Driess2, Kallol Ray1. 1. Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany. 2. Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany. 3. Case Center for Synchrotron Biosciences, NSLS-II, Brookhaven National Laboratory, Upton, NY, 11973, USA. 4. Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szent Gellért tér 4, 1111, Budapest, Hungary.
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)2 NiIII ]2+ complex and the decay of the asymmetric [NiIII (μ-O)2 CoIII ]2+ core through aromatic hydroxylation reactions represent a new domain for high-valent bis(μ-oxido)dimetal reactivity.
The strikingly different reactivity of a series of homo- and heterodinuclear [(MIII )(μ-O)2 (MIII )']2+ (M=n class="Chemical">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)2 NiIII ]2+ complex and the decay of the asymmetric [NiIII (μ-O)2 CoIII ]2+ core through aromatic hydroxylation reactions represent a new domain for high-valent bis(μ-oxido)dimetal reactivity.
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