Tetra- n -butylammonium difluorotriphenylsilicate (TBAT) is a conveniently handled anhydrous fluoride source, commonly used as a surrogate for tetra- n -butylammonium fluoride (TBAF). While prior studies indicate that TBAT reacts rapidly with fluoride acceptors, little is known about the mechanism(s) of fluoride transfer. We report on the interrogation of the kinetics of three processes in which fluoride is transferred from TBAT, in THF and in MeCN, using a variety of NMR methods, including chemical exchange saturation transfer, magnetisation transfer, diffusion analysis, and 1D NOESY. These studies reveal ion-pairing between the tetra- n -butylammonium and difluorotriphenylsilicate moieties, and a very low but detectable degree of fluoride dissociation, which then undergoes further equilibria and/or induces decomposition, depending on the conditions. Degenerate exchange between TBAT and fluorotriphenylsilane (FTPS) is very rapid in THF, inherently increases in rate over time, and is profoundly sensitive to the presence of water. Addition of 2,6-di- tert -butylpyridine and 3 Å molecular sieves stabilises the exchange rate, and both dissociative and direct fluoride transfer are shown to proceed in parallel under these conditions. Degenerate exchange between TBAT and 2-naphthalenyl fluorosulfate (ARSF) is not detected at the NMR timescale in THF, and is slow in MeCN. For the latter, the exchange is near-fully inhibited by exogenous FTPS, indicating a predominantly dissociative character to this exchange process. Fluorination of benzyl bromide (BzBr) with TBAT in MeCN- d 3 exhibits moderate progressive autoinhibition, and the initial rate of the reaction is supressed by the presence of exogenous FTPS. Overall, TBAT can act as a genuine surrogate for TBAF, as well as a reservoir for rapidly-reversible release of traces of it, with the relative contribution of the pathways depending, inter alia , on the identity of the fluoride acceptor, the solvent, and the concentration of endogenous or exogenous FTPS., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)