Synthesis and X-ray Crystal Structure Determination of First Examples of Donor-Functionalized Terphenyl Lanthanide Complexes

The molecular structures of novel donor-functionalized terphenyl derivatives of trivalent ytterbium, yttrium, and
samarium of composition [DanipYb(μ2-Cl)2(μ3-Cl)Li(THF)]2 (1) and [DanipLn(μ2-Cl)2(μ2-Cl)Li(THF)2]2 (Ln =
Y, 2; Ln = Sm, 3) are reported [Danip = 2,6-di(o-anisol)phenyl]. The complexes are obtained from the reaction
of equimolar amounts of DanipLi and LnCl3 (Ln = Yb, Y, Sm) in tetrahydrofuran at room temperature in 60%
yield. 1·2 toluene crystallizes in the monoclinic space group P1̄. Crystal data for 1·2 toluene at 203 K:  a =
9.7281(9) Å; b = 12.7989(12) Å; c = 13.4870(12) Å; α = 91.553(2)°; β = 103.957(2)°; γ = 109.916(2)°; V =
1521.2(2) Å3; Z‘ = 1; Dcalcd = 1.615 g cm-3; R1 = 3.43%. 2·toluene crystallizes in the monoclinic space group
P1̄. Crystal data for 2·toluene at 203 K:  a = 10.4152(10) Å; b = 12.5783(12) Å; c = 14.4640(14) Å; α =
69.963(2)°; β = 80.900(2)°; γ = 66.603(2)°; V = 1633.3(3) Å3; Z‘ = 1; Dcalcd = 1.386 g cm-3; R1 = 4.07%.
3·toluene crystallizes in the monoclinic space group P1̄. Crystal data for 3·toluene at 203 K:  a = 10.3457(8) Å;
b = 12.5658(10) Å; c = 14.4365(11) Å; α = 70.2250(10)°; β = 81.2820(10)°; γ = 66.8330(10)°; V = 1623.3(2)
Å3; Z‘ = 1; Dcalcd = 1.521 g cm-3; R1 = 3.40%. Complexes 1−3 represent first examples of donor-functionalized
terphenyl complexes of the elements ytterbium, yttrium, and samarium, respectively. The molecular structures of
1−3 feature a “constraint geometry” type arrangement of the Danip ligand at the lanthanide atom. The complexes
reported are dimeric and composed of lithium chloride bridged DanipLnCl2 moieties (Ln = Yb, Y, Sm), stabilized
through additional coordination of two methoxy functions to the lanthanide atom.