Is it possible to facilitate the formation of a genuine Be-Be or Mg-Mg single bond for the E species while it is in its neutral state? So far, (NHC )Be-Be(NHC ) (R=H, Me, Ph) have been reported where Be is in Δ excited state imposing a formal Be-Be bond order of two. Herein, we present the formation of a single E-E (E=Be, Mg) covalent bond in E (NHB ) (E=Be, Mg; NHB =(HCN ) B) complexes where E is in ∑ excited state having (nσ ) (nσ ) ((n+1)σ ) (n=2 for Be and n=4 for Mg) valence electron configuration and it forms electron-shared bonding with two NHB radicals. The effects of bonding with nσ and (n+1)σ orbitals will cancel each other, providing the former E-E bond order as one. Be (NHB ) complex is thermochemically stable with respect to possible dissociation channels at room temperature, whereas the two exergonic channels, Mg (NHB ) → Mg + Mg(NHB ) and Mg (NHB ) → Mg + (NHB ) , are kinetically inhibited by a free energy barrier of 15.7 and 18.7 kcal mol , respectively, which would likely to be further enhanced in cases of bulkier substituents attached to the NHB ligands. Therefore, the title complexes are first viable systems which feature a neutral E moiety with a single E-E covalent bond.
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