Carbon dioxide reduction by lanthanide(iii) complexes supported by redox-active Schiff base ligands

Here we have explored the ability of Schiff bases to act as electron reservoirs and to enable the multi-electron reduction of small molecules by lanthanide complexes. We report the reductive chemistry of the Ln(iii) complexes of the tripodal heptadentate Schiff base H(3)trensal (2,2 ',2 ''-tris(salicylideneimino)triethylamine), [Ln(III)(trensal)],1-Ln(Ln = Sm, Nd, Eu). We show that the reduction of the [Eu-III(trensal)] complex leads to the first example of a Eu(ii) Schiff base complex [{K(mu-THF)(THF)(2)}(2){Eu-II(trensal)}(2)],3-Eu. In contrast the one- and two-electron reduction of the [Nd-III(trensal)] and [Sm-III(trensal)] leads to the intermolecular reductive coupling of the imino groups of the trensal ligand and to the formation of one and two C-C bonds leaving the metal center in the +3 oxidation state. The resulting one- and two electron reduced complexes [{K(THF)(3)}(2)Ln(2)(bis-trensal)],2-Ln, and [{K(THF)(3)}(2){K(THF)}(2)Ln(2)(cyclo-trensal)],4-Ln(Ln = Sm, Nd) are able to effect the reductive disproportionation of carbon dioxide by transferring the electrons stored in the C-C bonds to CO(2)to selectively afford carbonate and CO. The selectivity of the reaction contrasts with the formation of multiple CO(2)reduction products previously reported for a U(iv)-trensal system.