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The combination of simple cobalt salts and N-heterocyclic carbene (NHC) ligands has been highly effective in C–H functionalization, hydroarylation and cross-coupling catalysis, though displaying a strong dependence on the identity of the NHC ligand. In addition, reactions effective with NHC ligands are often ineffective with phosphine ligands, further motivating the evaluation of the fundamental electronic structure and bonding differences in well-defined distorted tetrahedral Co(ii) complexes. Magnetic circular dichroism (MCD) studies indicate that Co(ii)–bisphosphines have larger ligand fields than Co(ii)–NHC complexes. Theoretical density functional theory (DFT) calculations were performed on an expanded set of L2CoCl2 complexes (L2 = NHC, bisphosphine and diamine) to study the electronic structure and relative ligation properties of NHCs compared to bisphosphine and diamine ligands. Mayer bond order and charge decomposition analyses indicate that NHC ligands are slightly stronger donor ligands than bisphosphines but also result in a weakening of Co–Cl bonds in a trans-like influence. From MCD and DFT studies, changing the NHC N-substituent has a larger effect on the ligand field of Co(ii)–NHC complexes than saturating the backbone. Overall, these studies provide detailed insight into the electronic structure and bonding effects in Co(ii) complexes with ligand types commonly explored in catalysis. [ABSTRACT FROM AUTHOR]