Revisiting the Bonding Scenario of Two Donor Ligand Stabilized C₂ Species

Quantum chemical calculations using density functional methods were performed for complexes of type L₂C₂ with L = NHC^Me (1), SNHC^Me (2) (S = saturated), cAAC^Me (3), and diamidocarbene (DAC^Me) (4). The equilibrium structures of 1-4 possess almost linear C₄ cores. A high thermochemical stability of the complexes with respect to dissociation, L₂C₂ → C₂ + 2L, is indicated by the large bond dissociation energy following the order 3 > 4 > 2 > 1. The results show that the use of SNHC^Me and DAC^Me as ligands is preferable over NHC^Me. The bonding analysis using charge and energy decomposition methods reveals that (cAAC^Me)₂C₂ and (DAC^Me)₂C₂ possess genuine cumulene C₄ moieties, which results from the electron-sharing bonding between quintet L₂ and quintet C₂ fragments. In contrast, the bonding in (NHC^Me)₂C₂ and (SNHC^Me)₂C₂ comes from a combination of dative and electron-sharing interactions between doublet L₂⁺ and doublet C₂^- fragments.