Alkaline Earth Metals Activate N(2) and CO in Cubic Complexes Just Like Transition Metals: A Conceptual Density Functional Theory and Energy Decomposition Analysis Study

Following the recent discovery of stable octa‐coordinated alkaline earth metals with N(2) and CO, the role of group II metals in the catalytic reduction of these ligands by means of density functional theory (DFT) calculations and conceptual DFT‐based reactivity indices is investigated. Cubic group IV and octahedral group VI transition metal complexes as well as the free ligands are computed for reference. The outer and most accessible atoms of N(2) and CO become much more nucleophilic and electrophilic in all complexes, relevant for N(2) fixation, as probed by the Fukui function and local softness. Within one row of the periodic table, the alkaline earth complexes often show the strongest activation. On the contrary, the electrostatic character is found to be virtually unaffected by complexation. Trends in the soft frontier orbital and hard electrostatic character are in agreement with calculated proton affinities and energy decomposition analyses of the protonated structures, demonstrating the dominance of the soft (HOMO–LUMO) orbital interactions.