Direct observation of reversible bond homolysis by 2D EXSY NMR

Bond homolysis is one of the most fundamental bond cleavage mechanisms. Thus, understanding of bond homolysis influences the development of a wide range of chemistry. Photolytic bond homolysis and its reverse process have been observed directly using time-resolved spectroscopy. However, direct observation of reversible bond homolysis remains elusive. Here, we report the direct observation of reversible Co-Co bond homolysis using two-dimensional nuclear magnetic resonance exchange spectroscopy (2D EXSY NMR). The characterization of species involved in this homolysis is firmly supported by diffusion ordered NMR spectroscopy (DOSY NMR). The unambiguous characterization of the Co-Co bond homolysis process enabled us to study ligand steric and electronic factors that influence the strength of the Co-Co bond. Understanding of these factors will contribute to rational design of multimetallic complexes with desired physical properties or catalytic activity.