Nature of Alkali- and Coinage-Metal Bonds versus Hydrogen Bonds

We have quantum chemically studied the structure and nature of alkali‐ and coinage‐metal bonds (M‐bonds) versus that of hydrogen bonds between A−M and B− in archetypal [A−M⋅⋅⋅B]− model systems (A, B=F, Cl and M=H, Li, Na, Cu, Ag, Au), using relativistic density functional theory at ZORA‐BP86‐D3/TZ2P. We find that coinage‐metal bonds are stronger than alkali‐metal bonds which are stronger than the corresponding hydrogen bonds. Our main purpose is to understand how and why the structure, stability and nature of such bonds are affected if the monovalent central atom H of hydrogen bonds is replaced by an isoelectronic alkali‐ or coinage‐metal atom. To this end, we have analyzed the bonds between A−M and B− using the activation strain model, quantitative Kohn‐Sham molecular orbital (MO) theory, energy decomposition analysis (EDA), and Voronoi deformation density (VDD) analysis of the charge distribution.
The same and not the same. Coinage‐metal bonds and, to a lesser extent, alkali‐metal bonds in [A−M⋅⋅⋅B]− model complexes are stronger than the corresponding hydrogen bonds in [A−H⋅⋅⋅B]−. Kohn‐Sham MO analyses reveal the origin of the responsible stronger electrostatic and orbital interactions.