Mo Fischer Carbene Complexes: A DFT Study on the Prediction of Redox Potentials

Abstract

The electronic properties of Fischer carbenes [Mo(CO)5−n(Ln){C(Y)Ar}] (n = 1–2, Ar = aryl group) can be tuned by changing the metal environment and their carbene substituents. The effect of substituting the carbonyl ligands of the carbenes, in the presence of Y = OEt, NH2 or NHCy as heteroatom substituent, on the redox potential and electronic properties of a series of experimentally known Mo carbenes has been examined using density functional theory methods, to get theoretical ways of predicting the experimental 1e− reduction (M−) and the 2e− oxidation potential. Several experimental redox potentials - theoretically calculated descriptor relationships were obtained that can be used to predict the reduction and the oxidation potential of the Mo Fischer carbene complexes.

Redox Chemistry of tris(β-diketonate)cobalt(III) Complexes: A Molecular View

“…Another descriptor that has been successfully used to determine the total electronic effect of ligands (eeL) on the metal they are coordinated to, [47][48][49] is the molecular electrostatic potential (MESP) on the metal. The MESP potential proved to be a powerful descriptor to predict redox potentials of mononuclear cobalt catalysts for hydrogen evolution reactions.…”