A New Domain of Reactivity for High-Valent Dinuclear [M(μ-O)b>2b>M′] Complexes in Oxidation Reactions

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• 作者：M. Sc. Xenia Engelmann ; Dr. Shenglai Yao ; Dr. Erik R. Farquhar ; Dr. Tibor Szilv&aacute ; si ; Dr. Uwe Kuhlmann ; Prof. Dr. Peter Hildebrandt ; Prof. Dr. Matthias Driess and Prof. Dr. Kallol Ray
• 刊名：Angewandte Chemie International Edition
• 出版年：2017
• 出版时间：January 2, 2017
• 年：2017
• 卷：56
• 期：1
• 页码：297-301
• 全文大小：1223K
• ISSN：1521-3773

文摘

The strikingly different reactivity of a series of homo- and heterodinuclear [(M^III)(μ-O)b>2b>(M^III)′]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 [(M^III)(μ-O)b>2b>(M^III)′]²⁺ core. In particular, the unprecedented nucleophilic reactivity of the symmetric [Ni^III(μ-O)b>2b>Ni^III]²⁺ complex and the decay of the asymmetric [Ni^III(μ-O)b>2b>Co^III]²⁺ core through aromatic hydroxylation reactions represent a new domain for high-valent bis(μ-oxido)dimetal reactivity.