Exploring the effect of the Ln(III)/Ln(II) redox potential on C-F activation and on oxidation of some lanthanoid organoamides.

The divalent europium complexes, and (L(Me/Et) = p-HC6F4N(CH2)2NMe2/Et2), have been prepared from redox-transmetallation/protolysis (RTP) reactions between Eu metal, Hg(C6F5)2 and L(Me/Et)H in thf. The complexes exhibit close (C)F-Ln interactions and the amide ligands feature tridentate N,N',F chelation. The complexes are thermally robust but on exposure to light they undergo C-F activation. From exposure of to light, the Eu(III) mixed fluoride/oxide cluster, was isolated, but other well-defined C-F activation products have proven elusive due to the stability of Eu(II). Oxidation of [Ln(L(R))2(thf)2] (Ln = Eu, R = Me; Ln = Yb, R = Et) with I2 afforded the heteroleptic iodo complexes, [Ln(L(R))2I(thf)n] (Ln = Eu, n = 1; Ln = Yb, n = 0), and the homoleptic complexes, [Ln(L(R))3]. The formation of the iodo complexes and the heteroleptic complexes appear to occur by different routes. shows interesting structural differences from reported [Ln(L(Et))3] (Ln = La, Ce, Nd) complexes, and highlights an incomplete shift towards N,N' chelation to the much smaller Yb ion. was prepared from a protolysis reaction between [Sm(CH2C6H4-NMe2-o)3] and L(Me)H. Heating a solution of in toluene at 110 °C for three days did not afford any samarium fluoride complex. An RTP reaction with Sm afforded the heteroleptic samarium complex, , in very low yield. From an attempted protolysis reaction between [Sm(DippForm)2(thf)2] and L(Me)H, the mixed ligand samarium fluoride complex, , was isolated. Overall, the instability of Sm(II) precludes control over the C-F activation reactions.