A convenient route to lanthanide triiodide THF solvates. Crystal structures of LnI(3)(THF)(4) [Ln = Pr] and LnI(3)(THF)(3.5) [Ln = Nd, Gd, Y].
A convenient route to lanthanide triiodide THF solvates. Crystal structures of LnI(3)(THF)(4) [Ln = Pr] and LnI(3)(THF)(3.5) [Ln = Nd, Gd, Y].
复制标题
制备镧系三碘化物 THF 溶剂化物的便捷途径。
作者：
K. Izod;S. Liddle;W. Clegg
1.5当量碘与粉末状稀土金属在THF中室温下反应，得到稀土三碘化物LnI（3）（THF）（n）（）。通过用THF对粗固体进行索格利特萃取进行纯化，可靠地得到作为微晶固体的THF加合物LnI（3）（THF）（4）[Ln = La，Pr]和LnI（3）（THF）（3.5）[Ln = Nd，Sm，Gd，Dy，Er，Tm，Y]。X射线晶体学显示，早期较大的镧系元素碘化物PrI（3）（THF）（4）结晶为具有五角双锥结构的离散分子，而后期较小的镧系元素碘化物LnI（3）（THF）（3.5）[Ln = Nd，Gd，Y]结晶为溶剂分离的离子对[LnI（2）（THF）（5）][LnI（4）（THF）（2）]其中在固态下，阳离子采用五边形双锥几何结构，阴离子采用八面体几何结构。
The reaction between 1.5 equiv of elemental iodine and rare earth metals in powder form in THF at room temperature gives the rare earth triiodides LnI(3)(THF)(n)() in good yields. Purification by Soxhlet extraction of the crude solids with THF reliably gives the THF adducts LnI(3)(THF)(4) [Ln = La, Pr] and LnI(3)(THF)(3.5) [Ln = Nd, Sm, Gd, Dy, Er, Tm, Y] as microcrystalline solids. X-ray crystallography reveals that the early, larger lanthanide iodide PrI(3)(THF)(4) crystallizes as discrete molecules having a pentagonal bipyramidal structure, whereas the later, smaller lanthanide iodides LnI(3)(THF)(3.5) [Ln = Nd, Gd, Y] crystallize as solvent-separated ion pairs [LnI(2)(THF)(5)][LnI(4)(THF)(2)] in which the cations adopt a pentagonal bipyramidal geometry and the anions adopt an octahedral geometry in the solid state.