Mechanisms of Oxidation‐Reduction Reactions Can Be Predicted by the Magnetic Isotope Effect

Abstract

Magnetic isotope effect can cause mass‐independent isotope fractionation, which can be used to predict the mechanisms of chemical reactions. In this critical paper, the isotope fractionation caused by magnetic isotope effect is used to understand detailed mechanisms of oxidation‐reduction reactions for some previously published experimental data. Due to the rule that reactions are allowed for certain electron spin state, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions due to the hyperfine interaction of the nuclear spin with the electron spin. It is demonstrated that compound or complex in paramagnetic (triplet) state accepts electrons during the reactions of electron transfer. Also, ligand field strength is responsible for the magnitude and the sign of the mass‐independent fractionation. From another side, magnetic isotope effect can be used to predict the ligand strength. According to the proposed mechanism, the following parameters are important for the sign and magnitude of mass‐independent isotope fractionation caused by magnetic isotope effect (due to predominant either singlet‐triplet or triplet‐singlet evolution): (i) the arrangement of the ligands around the metal ion; (ii) the nature (strength) of the ligands surrounding the metal ion; (iii) presence/absence of light. The suggested approach is applied to understand Hg reduction by dissolved organic carbon or by Sn(II).