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

To provide a better understanding of the recently published pure metalorganic NiI species, [Ni(cod)₂][Al(OR^F)₄] (1) [cod = 1,5- cyclooctadiene, R^F = 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 [Ni^II(THF)₆][Al(OR^F)₄]₂ (3) and Ni⁰. Further studies con- cerning 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. [ABSTRACT FROM AUTHOR]