The development of a workable electrochemical aryl sulfinate synthesis from the corresponding halide proved challenging stemming from the redox active nature of SO2 combined with its ability to interfere with Ni-catalysis. Unlike Ni-electrocatalytic amination or etherification reactions, which are redox neutral, sulfinylation is a net reductive process. By employing an electrochemical reaction mode, exogenous reductant can be replaced by electrons through the use of a sacrificial anode. Preliminary analysis of all constituents of the reaction (Ni catalyst, aryl halide, SO2) revealed that SO2 would be subject to preferential reduction with a mild reduction potential of only -0.78 V vs Ag/AgCl in CH3CN. This is particularly problematic because the reduced radical anion could dimerize to form dithionite dianion, or form aggregates with SO2. 51 Although super-stoichiometric SO2 could be employed to overcome this, excessive SO2 can poison Ni catalysts. Various SO2 surrogates have been developed and used over the last decade, however, their limited solubility in organic solvents at room temperature make them poor candidates for use in a simple electrochemical setup. Despite these concerns, optimization was deliberately focused on the use of SO2 in a stock solution (in dimethylacetamide, DMA) of controlled concentration (as determined by iodometry) due to its inexpensive nature and high solubility. In support of this choice, the use of SO2 solutions in electrochemical reactions have been documented in as early as 1960s, 52-55 and has recently been reviewed by Waldvogel. 25 Furthermore, SO2 readily forms Lewis adducts with amines, so a sterically hindered tertiary amine could in principle form an amine-SO2 complex in-situ to overcome issues of aggregation and catalyst poisoning. 56, 57 We began by evaluating the known Pd-catalyzed sulfinylation of aryl halides on substrate 1 (Table ). These conditions often require sterically hindered, electron-rich phosphine ligands, such as AmPhos 41, 42 and PAd2Bu 39, 43 which impede their effectiveness with ortho-substituted and electron-rich substrates. Not surprisingly, various reported Pd-catalyzed methods delivered the corresponding sulfinate 2 in only modest yield. Finally, no sulfinate product was detected using a Ni catalyst which was optimized for boronic acids. 14 With those background results in hand, attention turned to the development of a workable Ni-electrocatalytic solution.