Beryllium bonding: insights from the σ- and π-hole analysis

Abstract

Beryllium bonding is actually a subclass of secondary bonding. Similar to the case of halogen bonding, the σ-and π-holes on the Be atom of the monomers give in zeroth-approximation the direction of electrophilic attack favorable to the formation of beryllium bonds. The nature of beryllium bonding is purely electrostatic so that the SAPT energy decomposition perfectly explains the relevance of the polarization-and dispersion-contribution on the formation of the beryllium bond.

Noncovalent Bonds through Sigma and Pi-Hole Located on the Same Molecule. Guiding Principles and Comparisons

“…A particularly unusual combination of holes was examined by Alikhani [109]. The πhole on BeCl 2 occurs as a narrow belt around the Be atom, with V S,max = 32.2 kcal/mol.…”

“…As work has progressed, there has been recognition of π-holes as providing a means by which an aerogen bond (involving rare gas atoms) can form [100][101][102][103][104]. Other newly introduced types of σ/π-hole directed interactions are alkali and alkaline earth bond (e.g., beryllium bond, magnesium bond) in which atoms of 1st and 2nd groups contribute [105][106][107][108][109] or regium and spodium bonds which employ transition metals from 11th (regium [110][111][112][113][114][115]) or 12th (spodium [105,[116][117][118][119]) groups of the periodic table. The full range of these sorts of bonds, along with their designations, is summarized in Figure 1.…”

Linear BeNCO and OBeNC: kinetically stable neutral Be-bearing free molecules

“…Thus, they are extremely strong Lewis acids and can bond thermodynamically favorably with noble gases to form new complexes. 14,21,22 This result can explain the fact that when BeO binds with CN, product OBeNC is thermodynamically more stable than products BeOCN, BeONC, and OBeCN (Fig. 2 and Table S4, ESI†).…”

“…23 Even with noble gases, the combination reactions were found to be thermodynamically favorable. 14,22…”

Malonaldehyde-like Systems: BeF2 Clusters—A Subtle Balance between Hydrogen Bonds, Beryllium Bonds, and Resonance

“…Among them, aerogen [24], halogen [25,26], chalcogen [27][28][29][30], tetrel [31,32], triel [33,34], spodium [35], regium or coinage-metal [36][37][38][39], alkaline-earth [40,41], and alkalinebonds [42] have been described. Beryllium bonds [43,44], a subfamily of the alkaline-earth NCIs, were characterized more than a decade ago [43] and after then, the attention on them has grown in a very significant way [45][46][47][48][49][50].…”