Hitting the Bull's Eye: Stable HeBeOH+ Complex

It is now known that the heavier noble gases (Ng=Ar‐Rn) show some varying degrees of reactivity with a gradual increase in reactivity along Ar−Rn. However, because of their very small size and very high ionization potential, helium and neon are the hardest targets to crack. Although few neon complexes are isolated at very low temperatures, helium needs very extreme situations like very high pressure. Here, we find that protonated BeO, BeOH+ can bind helium and neon spontaneously at room temperature. Therefore, extreme conditions like very low temperature and/or high pressure will not be required for their experimental isolation. The Ng−Be bond strength is very high for their heavier homologs and the bond strength shows a gradual increase from He to Rn. Moreover, the Ng−Be attractive energy is almost exclusively originated from the orbital interaction which is composed of one Ng(s/pσ)→BeOH+ σ‐donation and two weaker Ng(pπ)→BeOH+ π‐donations, except for helium. Helium uses its low‐lying vacant 2p orbitals to accept π‐electron density from BeOH+. Previously, such electron‐accepting ability of helium was used to explain a somewhat stronger helium bond than neon for neutral complexes. However, the present results indicate that such π‐back donations are too weak in nature to decide any energetic trend between helium and neon. Thermochemically and kinetically stable NgBeOH+ (Ng=He‐Rn) complexes are presented where even the hardest targets (He and Ne) are found to form bonds with beryllium that are strong enough for them to be realized experimentally at room temperature.