Metal coordination complexes of the sterically hindered β-diketonate, 2,6-dimesitylbenzoyl pinacolone (esac), are reported for Co, Ni, Cu, and Zn. All four form ML2-type complexes with typical coordination behavior for late-metal β-diketonates, however the effects on established electrochemistry and reactivity vary somewhat per metal. For example, the striking chemical and electrochemical inertness of CoII(esac)2 to oxidation and disproportionation is atypical. Conversely, the behavior of CuII(esac)2 is rather typical relative to other CuII(β-diketonate)2 complexes. These data suggest a relative disfavoring of certain reaction pathways, and represent an important step in modulating the catalysis of the base metals via sterically hindered β-diketonates.