Lanthanoid Biphenolates as a Rich Source of Lanthanoid-Main Group Heterobimetallic Complexes

Several new trivalent dinuclear rare earth 2,2’-methylenebis(6-tert-butyl-4-methylphenolate) (mbmp²¯) complexes with the general form [Ln₂(mbmp)₃(thf)n] (Ln=Sm 1, Tb 2 (n=3), and Ho 3, Yb 4 (n=2), and a tetravalent cerium complex [Ce(mbmp)₂(thf)₂] (5) have been synthesised by RTP (redox transmetallation/protolysis) reactions from lanthanoid metals, Hg(C₆F₅)₂ and the biphenol mbmpH₂. These new complexes and some previously reported partially protonated rare earth biphenolate complexes [Ln(mbmp)(mbmpH)(thf)n] react with lithium, aluminium, potassium and zinc organometallic reagents to form lanthanoid-main group heterobimetallic species. When reaction mixtures containing the Ln biphenolate complexes were treated with n-butyllithium, both molecular ([Li(thf)₂Ln(mbmp)₂(thf)n] (Ln=La 6, Pr 7 (n=2) and Er 8, Yb 9, and Lu 10 (n=1)) and charge separated ([Li(thf)₄][Ln(mbmp)₂(thf)₂] (Ln=Y 11, Sm 12, Dy 13, and Ho 14) complexes were isolated. Treatment with trimethylaluminium also led to isolation of molecular ([AlMe₂Ln(mbmp)₂(thf)₂] (Ln=Pr 15, Sm 16, and Tb 17)) and ionic [La(mbmp)(thf)₅][AlMe₂(mbmp)] (18) complexes. One gadolinium-potassium ([K(thf)₃Gd(mbmp)₂(thf)₂] (19)), and one ytterbium-zinc species ([ZnEtYb(mbmp)₂(thf)] (20)) were isolated from treatment of reaction mixtures with potassium bis(trimethylsilyl)amide and diethylzinc respectively