Analyzing Mechanisms in Co(I) Redox Catalysis Using a Pattern Recognition Platform

29 September 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Redox catalysis has been broadly utilized in electrochemical synthesis due to its kinetic advantages over direct electrolysis. The appropriate choice of redox mediator can avoid electrode passivation and overpotential, which strongly inhibit the efficient activation of substrates in electrolysis. Despite the benefits brought by redox catalysis, establishing the precise nature of substrate activation remains challenging. Herein, we determine that a Co(I) complex bearing two N,N,N-tridentate ligands acts as a competent redox catalyst for the reduction of benzyl bromide substrates. Kinetic studies combining electroanalytical techniques with multivariable linear-regression analysis were conducted, disclosing an outer-sphere electron-transfer mechanism, which occurs in concert with C–Br bond cleavage. Furthermore, we apply a pattern recognition platform to distinguish between mechanisms in the activation of benzyl bromides, found to be dependent on the ligation state of the cobalt(I) center and ligand used.


redox catalysis mechanism
statistical modeling
reaction mechanisms
cyclic voltammetry

Supplementary materials

Out-Sphere ET SI for ChemRxiv


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