Tolman electronic parameter

The Tolman electronic parameter (TEP) is a measure of the electron donating or withdrawing ability of a ligand. It is determined by measuring the frequency of the A₁ C-O vibrational mode (ν(CO)) of a (pseudo)-C_3v symmetric complex, [LNi(CO)₃] by infrared spectroscopy, where L is the ligand of interest. [LNi(CO)₃] was chosen as the model compound because such complexes are readily prepared from tetracarbonylnickel(0).[1][2] The shift in ν(CO) is used to infer the electronic properties of a ligand, which can aid in understanding its behavior in other complexes. The analysis was introduced by Chadwick A. Tolman.

The A₁ "stretch" mode of Ni(CO)₃L used to determine the TEP of L.

The A₁ carbonyl band is rarely obscured by other bands in the analyte's infrared spectrum. Carbonyl is a small ligand so steric factors do not complicate the analysis. Upon coordination of CO to a metal, ν(CO) typically decreases from 2143 cm⁻¹ of free CO. This shift can be explained by π backbonding: the metal forms a π bond with the carbonyl ligand by donating electrons through its d orbitals into the empty π* anti-bonding orbitals on CO. This interaction strengthens the metal-carbon bond but also weakens the carbon-oxygen bond, resulting in a lower vibrational frequency. If other ligands increase the density of π electrons on the metal, the C-O bond is weakened and ν(CO) decreases further; conversely, if other ligands compete with CO for π backbonding, ν(CO) increases.