Abstract
The irreversible‐reduction potentials of 26 alkylcob(III)alamins (RCbl^III^ 1a–z) and 26 alkylcob(III)yrinates (R‘Cby’^III^; 2a–z) (E~p~ 1a–z and E~p~ 2a–z, resp.) have been measured in situ by single‐scan voltammetry of hydroxocob(III)alamin hydrochloride (vitamin B~12b~‐ HCl; 1) or heptamethyl cob(II)yrinate perchlorate (ClO~4~‘Cby’^II^; 2) in presence of the corresponding alkyl halides (RX;3a–z) in DMF. The reduction potentials of alkylcobalt complexes exhibiting half‐life times as short as a few seconds become measurable by this technique. Thermodynamic cycles prove that the observed reduction potentials are closely related to the standard reduction potentials E°(RCo^III^ + e^−^⇆R⋅ + Co^I^). Electron‐withdrawing groups and/or an increased degree of substitution at the Co‐bound C‐atom in RCbl^III^ and, R‘Cby’^III^ shift E~p~(1a–z) and E~p~ (2a–z) towards positive potentials. Linear correlations have been found between E~p~(1a–z) (E~p~(2a–z)) of RCbl^III^ (R‘Cby’^III^) and the p__K__~a~ of RH (or the Taft σ*‐ or the Hammett σ‐values of R) within each class of R, i. e. MeCbl^III^ (Me‘Cby’^III^), primary RCbl^III^ (R‘Cby’^III^) and secondary RCbl^III^ (R‘Cby’^III^). The correlations allow to distinguish between electronic effects of the Co‐bound alkyl residues and their steric interactions with the corrin side chains. The correlations have further been used to visualize the light‐induced formal insertion of an olefin into the Co, C‐bond of an alkylcobalamin (Scheme 2, 1a→1u), a key step in the vitamin‐B~12~‐catalized C, C‐bond formation.