C2 has attracted considerable attention from the scientific community for its debatable bonding situation. Herein, we show that the global minima of M2B2 and M3B2+ (M = Li, Na) possess similar covalent bonding patterns to C2. Because of strong charge transfer from M2/M3 to B2 dimer, they can be better described as [M2]2+[B2]2- and [M3]3+[B2]2- salt complexes with the B22- core surrounded perpendicularly by two and three M+ atoms, respectively. The energy decomposition analyses in combination with the natural orbital for chemical valence theory give four bonding components in C2, M2B2, and M3B2+ clusters. However, the fourth component does not arise from a bonding interaction but from polarization/hybridization. Considering the effect of Pauli repulsion in σ-space, the attractive covalent interaction in these molecules mainly comes from the two π-bonds. We further presented stable N-heterocyclic carbene (NHC) and triphenylphosphine (PPh3) ligands bound Li2B2(NHC)2 and Li2B2(PPh3)2 complexes. A comparative study of reactivity towards L = CO2, CO, and N2 between Li2B2(NHC)2 and B2(NHC)2 is also performed. L-Li2B2(NHC)2 is highly stable against L dissociation at room temperature for L = CO2 and CO, and the stability is markedly higher than that in L-B2(NHC)2. The larger B2→L π-backdonation in L-Li2B2(NHC)2 also makes L more activated than in L-B2(NHC)2.