Reversible Homolysis of Metal-Carbon Bonds

This article highlights the role of reversible homolytic metal-carbon bond cleavage processes in organometallic chemistry. Most considerations pertain to thermal bond activation. First, general aspects of the bond cleavage process, including the “persistent radical effect” and the determination/calculation of thermodynamic (bond dissociation enthalpy/free energy) and bond breaking/formation activation parameters, are critically analyzed. In three subsequent sections, attention is paid to the role of reversible metal-carbon bond cleavage in three different areas of chemistry: biochemistry, organic synthesis and controlled radical polymerization.