The europium hexafluoroacetylacetonate complex Eu(hfac)3(diglyme) was synthesized to examine its fluorescence and conversion to a Eu(II) analog. Reaction of Eu(hfac)3(diglyme) with potassium produced the unexpected trivalent product [EuF(hfac)3K(diglyme)]2. This reduction system was studied further by synthesizing other Ln(hfac)3(diglyme) analogs and examining their reactivity with potassium. The Nd, Sm, and Gd analogs of Ln(hfac)3(diglyme) also react with potassium to form [LnF(hfac)3K(diglyme)]2 as observed for europium. Reactions of the Eu(II) precursors, EuI2(thf)4 and {[Zr2(OiPr)9]Eu(μ-I)}2 with K(hfac) also form trivalent products, namely Eu(hfac)3(diglyme) and [Zr2(OiPr)9]Eu(hfac)2.