Pressure‐Assisted Formation of a Cobalt–Carbon σ Bond: A High‐Pressure Pulse Radiolysis Study

A distinctly negative reaction volume (−16.4 ± 1.6 cm³ mol⁻¹) characterizes reaction (a), which involves an almost pressure‐independent bond formation and a highly pressure‐decelerated bond breakage process. This indicates that pressure assists the formation of the cobalt–carbon σ‐bond by shifting the overall equilibrium to the right with increasing pressure. These results are discussed in terms of ligand substitution of Co^II and homolysis of Co^III‐complexes, respectively (nta = nitrilotriacetate). (Formula Presented.)