To better understand the role of the catalyst, in two separate experiments, 1-B and 1-Al were reacted with 3 equiv. of Me3Si-SPh. While in the case of 1-B no apparent reaction occurred, 1-Al reacted with Me3Si-SPh after 48h at 100 °C in C6D6 to produce a 3:1 mixture of 3-Al and 4-Al along with Me3Si-F as a side-product (Scheme 1). The latter was readily apparent from a [a] NMR yields measured by 19 F NMR spectroscopy using 1,2-difluorobenzene as an internal standard. Isolated yields in parentheses. Reactions run using 3 equiv. of Me3Si-SPh. were not active catalysts for the reaction of Et3SiH with pentafluoropyridine under the catalytic conditions established for Me3Si-SPh. Following an extensive screen of conditions and additives it was found that 10 mol% NaBAr F could be used as an additive to effectively promote the reaction.