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A new option for stabilizing unusual Ln 2+ ions has been identified in the reaction of Cp' 3 Ln, 1-Ln (Ln = La, Ce; Cp' = C 5 H 4 SiMe 3 ), with potassium graphite (KC 8 ) in benzene in the presence of 2.2.2-cryptand. This generates [K(2.2.2-cryptand)] 2 [(Cp' 2 Ln) 2 (μ-η 6 :η 6 -C 6 H 6 )], 2-Ln , complexes that contain La and Ce in the formal +2 oxidation state. These complexes expand the range of coordination environments known for these ions beyond the previously established examples, (Cp'' 3 Ln) 1- and (Cp' 3 Ln) 1- (Cp'' = C 5 H 3 (SiMe 3 ) 2 -1,3), and generalize the viability of using three anionic carbocyclic rings to stabilize highly reactive Ln 2+ ions. In 2-Ln , a non-planar bridging (C 6 H 6 ) 2- ligand shared between two metals takes the place of a cyclopentadienyl ligand in (Cp' 3 Ln) 1- . The intensely colored ( ε = ∼8000 M -1 cm -1 ) 2-Ln complexes react as four electron reductants with two equiv. of naphthalene to produce two equiv. of the reduced naphthalenide complex, [K(2.2.2-cryptand)][Cp' 2 Ln(η 4 -C 10 H 8 )].

chemical science

Isolation of +2 rare earth metal ions with three anionic carbocyclic rings: bimetallic bis(cyclopentadienyl) reduced arene complexes of La<sup>2+</sup> and Ce<sup>2+</sup> are four electron reductants

Isolation of +2 rare earth metal ions with three anionic carbocyclic rings: bimetallic bis(cyclopentadienyl) reduced arene complexes of La2+ and Ce2+ are four electron reductants

Isolation of +2 rare earth metal ions with three anionic carbocyclic rings: bimetallic bis(cyclopentadienyl) reduced arene complexes of La²⁺ and Ce²⁺ are four electron reductants