Metal-ligand bond lengths and strengths: are they correlated? A detailed CSD analysis

Structure data on metal-alkoxides, metal-alcohol, metal-carboxylates, metal-carboxylic acid, metal-azolate and metal-azole coordination compounds from the Cambridge Structural Database (CSD) were analysed in terms of bond lengths. In general the anionic ligands form shorter metal-ligand bonds by about 0.02-0.05 angstrom compared to neutral ligands, a clear indication of a charge contribution to the bonding interactions. This small difference is not, however, deemed as sufficient to generate two distinct classes of metal-ligand bonding. Instead, the anionic ligands can be viewed as having charge assisted metal-ligand bonding, corresponding to the same term used for charge-assisted hydrogen bonding.