With the established optimized conditions for aryl sulfinate synthesis, the substrate scope was explored. To improve the handling of the sulfinylated product, all sulfinates were fluorinated and isolated as sulfonyl fluorides (Table ). In general, the Ni-catalyzed electrochemical sulfinylation, i.e. e-sulfinylation, works well on aryl iodides with various electron-donating and withdrawing groups, with a great tolerance to different substituents, particularly at the orthoposition (a notable limitation in Pd-catalyzed sulfinylation). Electron-deficient aryl bromides were also successfully converted into sulfinates and isolated as sulfonyl fluorides. Aryl sulfonyl fluorides substituted with one or more electron-donating groups, such as methyl groups (4 and 5), methoxy ethers (6-8), a 1,3-benzodioxole (9), a 2-amino group , and a tert-butyl carbamate were isolated in modest to good yields. Electron-neutral substrates, such as 2-thioanisole (3) and 2-biphenyl were also converted effectively. For comparison, established Pd conditions were also performed on these substrates, yet these usually only resulted in poor to modest yields, as determined by 19 F-NMR spectroscopy. In particular, the ortho-substituted thioanisole (3) and aniline were poor substrates in Pd-catalysis, possibly due to their coordination to Pd. In contrast, this was not the case in e-sulfinylation, as both substrates were able to deliver sulfonyl fluorides in good 60% and 51% yields, respectively. Next, a series of sulfonyl fluorides were synthesized electrolytically from electron-deficient aryl iodides, showing good tolerance to a range of functional groups, including reductively labile halides, such as F (13), Cl , and Br , amide , trifluoromethyl , 2-methylbenzothiazole , ketone , ester , carboxylic acid , and nitrile . Whilst state-of-the-art Pd catalysis performed comparably, and sometimes better, on these substrates, the synthesis of 19 and 23 were unsuccessful, likely due to their Lewis basicity. Notably, when 1-bromo-4-iodobenzene was employed, excellent chemoselectivity was achieved with Ni-catalyzed e-sulfinylationonly the iodide was converted into sulfinate, then sulfonyl fluoride 15. The C-Br bond remained intact and no 4-iodobenzenesulfonyl fluoride 15a was detected; in contrast, poor selectivity between the bromide and iodide was observed under both benchmarked Pd conditions, resulting in a mixture of 15 and 15a, which have similar polarity and hence are difficult to separate.