title: A New Domain of Reactivity for High-Valent Dinuclear [M(μ-O)2M'] Complexes in Oxidation Reactions.
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.
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany.
authors.forename: Xenia
authors.initials: X
authors.lastname: Engelmann
authors.affiliation: Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Shenglai
authors.initials: S
authors.lastname: Yao
authors.affiliation: Case Center for Synchrotron Biosciences, NSLS-II, Brookhaven National Laboratory, Upton, NY, 11973, USA.
authors.forename: Erik R
authors.initials: ER
authors.lastname: Farquhar
authors.affiliation: Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szent Gellért tér 4, 1111, Budapest, Hungary.
authors.forename: Tibor
authors.initials: T
authors.lastname: Szilvási
authors.affiliation: Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Uwe
authors.initials: U
authors.lastname: Kuhlmann
authors.affiliation: Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Hildebrandt
authors.affiliation: Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Driess
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489, Berlin, Germany.
authors.forename: Kallol
authors.initials: K
authors.lastname: Ray
mesh_terms: D003035:Cobalt / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D056831:Coordination Complexes; D003035:Cobalt; D009532:Nickel; D007501:Iron; D010100:Oxygen
keywords: NIH shift; dioxygen activation; heterobimetallic complex; metal-oxo complexes; nucleophilic oxidant