SF6 can be prepared from the elements through exposure of S8 to F2. This was also the method used by the discoverers Henri Moissan and Paul Lebeau in 1901. Some other sulfur fluorides are cogenerated, but these are removed by heating the mixture to disproportionate any S2F10 (which is highly toxic) and then scrubbing the product with NaOH to destroy remaining SF4 .
There is virtually no reaction chemistry for SF6. A main contribution to the inertness of SF6 is the steric hindrance of the sulfur atom, whereas its heavier group 16 counterparts, such as SeF6 are more reactive than SF6 as a result of less steric hindrance (See hydrolysis example). It does not react with molten sodium, but reacts exothermically with lithium.
For example, reactions of SF6 with water to produce sulfuric acid and hydrofluoric acid (a hydrolysis reaction, which would be thermodynamically favourable) does not occur as a result of steric hindrance: SF6 + 4H2O(l) → no reaction