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Reactivity of [Ni(cod)2][Al(ORF)4] towards Small Molecules and Elements

Miriam M. Schwab, Daniel Himmel, Sylwia Kacprzak, Valentin Radtke, Daniel Kratzert, Zeinab Yassine, Philippe Weis, Stefan Weber, and Ingo Krossing*

Z. anorg. allg. Chem. 2018, 644, 50-57


To provide a better understanding of the recently published pure metalorganic NiI species, [Ni(cod)2][Al(ORF)4] (1) [cod = 1,5‐cyclooctadiene, RF = C(CF3)3], further characterizations were performed and analyzed. Thus, the solvation of 1 in THF was examined by EPR, surprisingly disclosing the initiation of a disproportionation reaction to [NiII(THF)6][Al(ORF)4]2 (3) and Ni0. Further studies concerning the ability of 1 to activate small molecules exhibit the formation of a remarkable [Ni3S2(cod)3]2+ cluster (5) in an oxidation reaction with S8, while EPR measurements of the resulting product in a reaction with oxygen indicate a possible coordination of O2. Single crystal X‐ray structures as well as spectroscopic analyses of 3 and 5 are described.


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