Abstract
AbstractFirst‐row transition metal complexes have garnered attention due to their ability to activate aliphatic halides for catalytic cross‐coupling reactions. However, mechanistic investigation of these systems is challenging as a consequence of difficulties associated with preparing the relevant metal complexes and the resultant poor stability of such intermediates for subsequent analytical interrogation. In this context, we have developed a platform to rapidly measure kinetic data using electroanalytical methods, which facilitates a wide range of physical organic studies. As a result, we have investigated and compared the reaction of benzyllic halides with electrogenerated MnI(PyBox)Cl, FeI(Pyrox)OTf, CoI(Pyrox)Br, CoI(PyBox)Br, NiI(Phox)Br complexes. The experimental results support a unified inner‐sphere halogen atom abstraction mechanism for these different complexes while also providing the ability to directly compare through multivariate linear regression analyses the subtle differences imparted by metal/ligand combinations. The information gleaned by this study has implications why certain metal complexes are matched to oxidative addition processes relevant in catalytic processes.
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