Computational Study of sp^x (x=1-3)-Hybridized Be-Be Bonds Stabilized by Amidinate Ligands

Complexes containing odd-electron Be-Be bonds are still rare until now. Hereby, a series of neutral di-beryllium amidinate complexes containing a Be-Be bond were explored theoretically. The complexes with direct chelation with the Be₂ dimer by the bidentate amidinate (AMD) ligands are always corresponding to their global minimum structures. The detailed bonding analyses reveal that the localized electrons of the Be-Be fragment can be adjusted by the amount of AMD ligands because each AMD ligand only takes one electron from the Be₂ fragment. Meanwhile, the hybridization of the central Be atom also changes as the number of AMD ligands increases. In particular, the sp³ -hybridized single-electron Be-Be bond is firstly identified in the tri-AMD-ligands-chelated neutral D_3h -Be₂ (AMD)₃ complex, which also possesses the higher stability compared to its monoanionic D_3h -Be₂ (AMD)₃ ^- and monocationic C₃ -Be₂ (AMD)₃ ⁺ analogues. Importantly, our study provides a new approach to obtain a neutral odd-electron Be-Be bond, namely by the use of radical ligands through side-on chelation.