The optimization of an electrocatalytic reaction is not as complicated as it may seem. 70, 71 Although numerous variables not associated with canonical organic methodology need to be evaluated such as electrode, electrolyte, and current, the results are independently optimizable. Thus, keeping all variables constant, the individual variables can be systemically optimized and combined to give higher yields. A graphical summary is presented in Table to show representative reaction permutations from the entire optimization process. To highlight a few important factors, it was found that 3 equiv of TBABr was needed to produce sulfinate in a good yield. While SO2 is capable to form Lewis adduct with amines in a 1:1 ratio, 0.5 equiv of DIPEA with 2 equiv of SO2 elicited a marginally higher yield. This is likely due to the instability of DIPEA-SO2 adduct 72 allowing a rapid equilibrium between the Lewis adduct and free SO2, while preventing aggregation between SO2 and its radical anion. CH3CN was found to be the best solvent, but when an acetonitrile stock solution of SO2 was used, an impermeable black passivation layer was formed on the Zn anode, which eventually insulates the electrode and halts the electrolysis. In contrast, when a DMA stock solution was employed, deposits forming at the electrode peeled off leading to the choice of a 9:1 CH3CN/DMA mixture as reaction solvent. Control experiments have shown that all of the components are necessary for a successful sulfinylation. Omission of the Ni catalyst or DIPEA resulted in no sulfinate formation. Electricity is also needed for the reaction to proceed, as no sulfinate was formed when stirred with Zn dust. Inspired by a recent report on the use of perylene bisimide mediators 73 in facilitating reductive reactions, such compounds were also screened (see supporting information for list). From that study the addition of NMPI was found beneficial, where its absence led to a drastic drop in yield. When Selectfluor or NFSI was employed in fluorination, which is commonly employed to convert sulfinates into sulfonyl fluorides, little sulfonyl fluoride 3 was detected. This is likely due to the high concentration of other halides (Br and I) in the pot which can compete with sulfinate for oxidation. As increasing the amount of the fluorinating agents up to 4 equiv was found to be ineffective, more cost-effective options were pursued using TBAF as a fluoride source and NCS as an oxidant (4 equiv each). This delivered the sulfonyl fluoride 3 in 61% NMR yield (60% isolated), which is comparable to the sulfinylation HPLC yield (63%).