Di-zirconium-nona-isopropoxide as a cyclopentadienyl replacement: synthesis and crystal structure of the di-zirconium-nona-isopropoxide lanthanide halides {[Zr2(OPri)9]Eu(μ-I)}2, {[Zr2(OPri)9]NdCl(μ-Cl)}2 and {[Zr2(OPri)9]Nd(μ-O2CBut)(μ-Cl)}2 †

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Abstract

Structural evidence has been obtained which suggests that the monoanionic polydentate moiety, Zr2(OPri)9–, obtainable from KZr2(OPri)9 and Zr2(OPri)8(PriOH)2, can function as a replacement for cyclopentadienyl-containing ligand sets in established types of organolanthanide compounds. The Zr2(OPri)9– unit has been found to replace the ligand set [(C5Me5)(thf)2]– (thf = tetrahydrofuran) in [(C5Me5)(thf)2Sm(µ-I)]2 and the ligand set [(C5H5)2]2– in [(C5H5)2Nd(thf)(µ-Cl)]2. The complex KZr2(OPri)9 reacts with LnI2(thf)2 (Ln = Eu or Sm) in toluene to form the isostructural, isomorphous complexes {[Zr2(OPri)9]Ln(µ-I)}2, which crystallize from toluene (1: {[Zr2(OPri)9Eu(µ-I)}2, P21/n, a = 12.082(2), b = 19.309(3), c = 17.294(3) Å, β = 92.805(11)°, U = 4029.4(12) Å3 and Dc = 1.637 g cm–3 for Z = 2; 2: {[Zr2(OPri)9]Sm(µ-I)}2, P21/n, a = 12.071(2), b = 19.273(3), c = 17.279(2) Å, β = 92.679(12)°, U = 4015.4(8) Å3 and Dc = 1.640 Mg m–3 for Z = 2). The face-sharing bioctahedral Zr2(OPri)9– unit uses two of its central isopropoxide ligands and one additional isopropoxide on each zirconium to attach to the lanthanide metal, which has a distorted octahedral co-ordination environment completed by two bridging iodide ligands. The complex Zr2(OPri)8(PriOH)2 reacts with NdCl3 in thf to form {[Zr2(OPri)9]NdCl(µ-Cl)}2 3, which crystallizes from toluene [C2/c, a = 25.283(5), b = 12.505(3), c = 18.162(2) Å, β = 119.802(9)°, U = 8553.6(22) Å3 and Dc = 1.515 Mg m–3 for Z = 4]. In 3 the Zr2(OPri)9– unit again functions as a tetradentate ligand as in 1 and 2. Two bridging and one terminal chloride complete the pentagonal bipyramidal environment of Nd. A derivative of 3 in which the terminal chlorides are replaced by bridging pivalate groups is obtained by reacting NdCl3 with KO2CBut and Zr2(OPri)8(PriOH) in thf to form {[Zr2(OPri)9]Nd(µ-O2CBut)(µ-Cl)}2 4, which crystallizes from toluene [P, a = 12.267(3), b = 14.217(4), c = 14.700(3) Å, α = 88.08(2), β = 71.98(2), γ = 78.37(2)°, U = 2386.7(10) Å3 and Dc = 1.485 Mg m–3 for Z = 1].

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