Unexpected Reaction of 2,2′‐Bipyridyl‐cycloocta‐1,5‐diene‐nickel(0) with Acetone and Dioxygen

The reaction of (bipy)Ni(cod) ( 1 ) (bipy = 2,2′‐bipyridyl, cod = cycloocta‐1,5‐diene) with dioxygen and acetone at ?20°C affords (bipy)Ni(C₉H₁₆O₃) ( 2 ) (C₉H₁₆O₃^2— = 2,4,6,6‐tetramethyl‐tetrahydropyran‐2,4‐diolate), which has been characterized by NMR, MS and an X‐ray crystal structure determination. Acidolysis of compound 2 with two equivalents of acetyl acetone (Hacac) yields (bipy)Ni(acac)₂ and C₉H₁₈O₃ ( 3 ) (2,4,6,6‐tetramethyl‐tetrahydropyran‐2,4‐diol), a cyclic trimer of acetone.