Lanthanide Trifluoromethanesulfonates - Synthesis

Synthesis

Lanthanide triflates are synthesized from lanthanide oxide and aqueous triflic acid. In a typical preparation, a 1:1 (v/v) solution of trilfic acid in water is added to a slight stoichiometric excess of lanthanide oxide. The mixture is stirred and heated at 100 °C for a few hours, and the excess lanthanide oxide is filtered off. The excess oxide ensures all of the triflic acid is consumed. The water is removed under reduced pressure (or simply boiled away) to leave a hydrated lanthanide triflate, Ln(H2O)9(OTf)3.

In simplified form the reaction is

Ln2O3 + 6HOTf → 2Ln(OTf)3 + 3H2O

Since the reaction takes place in aqueous solution, more accurately,

Ln2O3 + 6HOTf + 18H2O → 2(OTf)3 + 3H2O

Anydrous lanthanide triflates can be produced by dehydrating their hydrated counterparts by heating between 180 and 200 °C under reduced pressure for 48 hrs. This is a major advantage of lanthanide triflates compared to lanthanide halides, whose anhydrous forms require more tedious synthetic procedures because they cannot be obtained by dehydrating their hydrates (because of oxyhalide formation).

(OTf)3 → Ln(OTf)3 + 9H2O (180-200 °C, ~10−2 - 10−4 torr, 48 hrs)

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