Heteroleptic Lanthanide Complexes with Aryloxide Ligands. Synthesis and Structural Characterization of Divalent and Trivalent Samarium Aryloxide/Halide and Aryloxide/Cyclopentadienide Complexes

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Abstract
Synthesis of a new class of heteroleptic samarium aryloxide complexes has been achieved by the use of homoleptic samarium(II) bis(aryloxide) Sm(OAr)2(THF)3 (1, Ar = C6H2But2-2,6-Me-4) as a starting material, which is easily obtained by reaction of Sm(N(SiMe3)2)2(THF)2 with 2 equiv of ArOH in THF. 1 reacts with 1 equiv of SmI2 in THF to give Sm(II) mixed aryloxide/iodide [(ArO)Sm(μ-I)(THF)3]2 (2), which adopts a dimeric structure via very weak Sm···I (3.534(2) Å) interactions. Reaction of 2 with C5Me5K in THF/HMPA affords the corresponding Sm(II) aryloxide/cyclopentadienide (C5Me5)Sm(OAr)(HMPA)2 (3). Oxidation of 1 with 0.5 equiv of I2 in THF gives monomeric samarium(III) aryloxide/iodide (ArO)2SmI(THF)2 (4), while the similar reaction of 1 with ClCH2CH2Cl or tBuCl in THF affords dimeric samarium(III) aryloxide/chloride [(ArO)2Sm(μ-Cl)(THF)]2 (5). Crystal data for 1: monoclinic, space group P21, a = 9.903(3) Å, b = 16.718(5) Å, c = 13.267(2) Å, β = 95.17(2)°, V = 2187(2) Å3, Z = 2, Dc = 1.223 g cm-3, R = 0.0634. Crystal data for 2·2THF: monoclinic, space group P21/a, a = 18.330(6) Å, b = 14.320(4) Å, c = 13.949(3) Å, β = 103.16(2)°, V = 3563(2) Å3, Z = 2, Dc = 1.46 g cm-3, R = 0.0606. Crystal data for 3: triclinic, space group P1̄, a = 10.528(1) Å, b = 12.335(2) Å, c = 19.260(2) Å, α = 101.33(1)°, β = 95.230(9)°, γ = 108.54(1)°, V = 2293.1(5) Å3, Z = 2, Dc = 1.25 g cm-3, R = 0.0358. Crystal data for 4: monoclinic, space group C2/c, a = 17.191(7) Å, b = 10.737(6) Å, c = 21.773(7) Å, β = 98.80(3)°, V = 3971(3) Å3, Z = 4, Dc = 1.44 g cm-3, R = 0.0467. Crystal data for 5: monoclinic, space group P21/n, a = 13.750(3) Å, b = 17.231(3) Å, c = 14.973(6) Å, β = 95.81(2)°, V = 3529(2) Å3, Z = 2, Dc = 1.31 g cm-3, R = 0.0557.

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