A Model for the Prediction of the Redox Potentials in [FeFe]‐Clusters from the Electronic Properties of Isocyanide Ligands

Using an experimental‐computational methodology, arylisocyanides (CNAr) have shown to be excellent probes to study the effect of electronic properties in the electrochemical behavior of [FeFe]‐complexes. The calculated LUMO distribution of p‐ substituted [Fe 2 {(μ‐SCH 2 ) 2 N t Bu}(CO) 5 (CNAr)] complexes ( 2 ) show that, depending on the substituent, the first reduction event ( E pc ) may be metal centered or ligand centered. The electrochemical response of complexes 2 has been experimentally studied and correlated to the calculations performed. The E pc values were found to directly correlate to different spectroscopic properties such as IR and 13 C{ 1 H} NMR spectroscopies. These findings could be used to predict the E pc values of new [FeFe]‐complexes.