Structural and Electronic Influences on Rates of Tertpyridine-Amine Co^III -H Formation During Catalytic H₂ Evolution...

In this work, the differences in catalytic performance for a series of Co hydrogen evolution catalysts with different pentadentate polypyridyl ligands (L), have been rationalized by examining elementary steps of the catalytic cycle using a combination of electrochemical and transient pulse radiolysis (PR) studies in aqueous solution. Solvolysis of the [Co^II -Cl]⁺ species results in the formation of [Co^II (κ⁴ -L)(OH₂ )]²⁺ . Further reduction produces [Co^I (κ⁴ -L)(OH₂ )]⁺ , which undergoes a rate-limiting structural rearrangement to [Co^I (κ⁵ -L)]⁺ before being protonated to form [Co^III -H]²⁺ . The rate of [Co^III -H]²⁺ formation is similar for all complexes in the series. Using E_1/2 values of various Co species and pK_a values of [Co^III -H]²⁺ estimated from PR experiments, we found that while the protonation of [Co^III -H]²⁺ is unfavorable, [Co^II -H]⁺ reacts with protons to produce H₂ . The catalytic activity for H₂ evolution tracks the hydricity of the [Co^II -H]⁺ intermediate.