A series of rare earth complexes of the form Ln(L^R)₃ supported by bidentate ortho-aryloxide-NHC ligands are reported (L^R = 2-O-3,5-^tBu₂-C₆H₂(1-C{N(CH)₂N(R)})); R = ⁱPr, ^tBu, Mes; Ln = Ce, Sm, Eu). The cerium complexes cleanly and quantitatively insert carbon dioxide exclusively into all three cerium carbene bonds, forming Ce(L^R·CO₂)₃. The insertion is reversible only for the mesityl-substituted complex Ce(L^Mes)₃. Analysis of the capacity of Ce(L^R)₃ to insert a range of heteroallenes that are isoelectronic with CO₂ reveals the solvent and ligand size dependence of the selectivity. This is important because only the complexes capable of reversible CO₂-insertion are competent catalysts for catalytic conversions of CO₂. Preliminary studies show that only Ce(L^Mes·CO₂)₃ catalyses the formation of propylene carbonate from propylene oxide under 1 atm of CO₂ pressure. The mono-ligand complexes can be isolated from reactions using LiCe(NⁱPr₂)₄ as a starting material; LiBr adducts [Ce(L^R)(NⁱPr₂)Br·LiBr(THF)]₂ (R = Me, ⁱPr) are reported, along with a hexanuclear N-heterocyclic dicarbene [Li₂Ce₃(OArC^Me-H)₃(NⁱPr₂)₅(THF)₂]₂ by-product. The analogous para-aryloxide-NHC proligand (p-L^Mes = 4-O-2,6-^tBu₂-C₆H₂(1-C{N(CH)₂NMes}))) has been made for comparison, but the rare earth tris-ligand complexes Ln(p-L^Mes)₃(THF)₂ (Ln = Y, Ce) are too reactive for straightforward Lewis pair separated chemistry to be usefully carried out.

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