The fluoride ion is important to synthetic chemistry, often because it can be used to cleave silyl ethers (the silicon analogue of a carbon ether). Fluoride is notorious for holding onto water (like any tiny ion - lithium is about as bad), so even an "anhydrous" solution of TBAF in (say) THF will often contain ca 5% water. The less water you have, the more "naked" fluoride anion you have, which is much, much more reactive than aquated fluoride.
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very interesting...great blog, too bad i only discovered it recently.