Alkaline Earth Metals Activate N2 and CO in Cubic Complexes Just Like Transition Metals: A Conceptual Density Functional Theory and Energy Decomposition Analysis Study. Issue 56 (6th September 2020)

• Record Type: Journal Article
• Authors: Bettens, Tom; Pan, Sudip; De Proft, Frank; Frenking, Gernot; Geerlings, Paul
• Is Part Of: Chemistry. Volume 26:Issue 56(2020)
• Page Start: 12785
• Page End: 12793
• Publication Date: 2020-09-06
• Subjects: alkaline earth metals -- conceptual DFT -- density functional calculations -- energy decomposition analysis -- nitrogen fixation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202001585
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Following the recent discovery of stable octa‐coordinated alkaline earth metals with N2 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 N2 and CO become much more nucleophilic and electrophilic in all complexes, relevant for N2 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. Abstract : Alkaline earth complexes : The viability of alkaline earth metal‐based N2 fixation is investigated. It is shown that the activation of N2 through complexation originates from the d–π back‐donation. Within one row of the periodic table, the alkaline earth metal shows the strongest nucleophilic activation of the N2 ligand, confirming clear trends in proton affinities.