STRUCTURAL DIVERSITY IN SOLVATED LANTHANIDE HALIDE-COMPLEXES
STRUCTURAL DIVERSITY IN SOLVATED LANTHANIDE HALIDE-COMPLEXES
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DOI：
10.1021/ic00107a009
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发表时间：
1995-02-01
影响因子：
4.6
通讯作者：
DOEDENS, RJ
中科院分区：
文献类型：
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作者：
EVANS, WJ;SHREEVE, JL;DOEDENS, RJ
从纯ε-己内酯 (C6H10O2) 和己内酯/THF 混合物中结晶出的三氯化镧系元素，揭示了溶剂化三氯化镧系元素复合物的结构化学性质比之前观察到的更加多样化。由于金属不同，不同的产物在相同条件下优先结晶，产生一系列复合物，其组成随着径向尺寸的函数而变化并不平滑。以下化合物按金属径向尺寸递增的顺序进行了结构表征：YbCl3(C6H10O2)(THF)(2), 1； YCl3(C6H10O2)(3), 2; [TbCl4(THF)(2)](-)[TbCl2(THF)(5)](+), 3; [Cl3Sm(mu-Cl)(3)SmCl3](3-)[Sm(C6H10O2)(8)](3+),4; [Cl3Nd(mu-Cl)(3)NdCl3](3-)[Nd(C6H10O2)(8)](3+) 5. 在这些研究过程中，还通过以下方法鉴定了聚合卤化物 [NdCl(mu-Cl)(2)(THF)(2)](n), 6 和 [CeCl(mu-Cl)(2)(THF)(2)](n), 7 X射线晶体学。尽管 1 和 2 都具有八面体几何形状，但它们的不同之处在于己内酯的含量以及 1 是面状而 2 是子午面这一事实。离子对系统3包含具有反式八面体几何形状的六配位阴离子和具有五角双锥结构中的轴向氯配体的七配位阳离子。配合物4和5含有不含己内酯的双金属三阴离子，其采用共面双八面体几何形状。 4和5中的八配位阳离子不含氯配体，并采用方形反棱镜几何形状。同构结构 6 和 7 含有七配位五角双锥金属中心，周围环绕着四个桥接氯原子、一个末端氯原子和两个末端 THF 配体。 YbCl3(C6H10O2)(THF)(2), 1，从ε-己内酯/THF中结晶，空间群 P2(1)/n [C-2h(5)； No. 14] 其中 a = 11.580(2) Angstrom，b = 12.802(3) Angstrom，c = 13.532(3) Angstrom，beta = 103.462(15) 度，V = 1951.0(7) Angstrom(3)，D-calcd = 1.831 Mg/m(3)，Z = 4. 基于 3894 次反射 (\F-0\ > 3.0 sigma(\F-0\)) 的模型最小二乘细化收敛至 R(F) = 3.5%。 YCl3(C6H10O2)(3), 2，由ε-己内酯/THF和纯ε-己内酯在空间群P (1)中结晶而成，a = 10.083(1) Angstrom，b = 11.706(1) Angstrom，c = 11.702(1) Angstrom，α = 60.071(7) 度，beta = 81.274(9) 度，gamma = 75.741(8) 度，V = 1159.4(2) Angstrom(3)，Z = 2 时 D-calcd = 1.540 Mg/m(3)。基于 4846 个观察到的反射对模型进行最小二乘细化 (\F-0\ > 2.0 sigma(\F-0\)) 收敛到 R(F) = 4.0%。 [TbCl4(THF)(2)](-)[TbCl2(THF)(5)](+), 3，从ε-己内酯/THF 结晶，空间群 C2/c [C-2h(6),； No. 15] 其中 a = 12.401(2) Angstrom，b = 11.420(2) Angstrom，c = 27.413(3) Angstrom，beta = 91.100(11) 度，V = 3881.4(9) Angstrom(3)，D-calcd = 1.772 Mg/m(3)，Z = 8. 基于 3936 次反射 (\F-0\ > 3.0 sigma(\F-0\)) 的模型最小二乘细化收敛至 R(F) = 3.4%。通过晶胞测定发现[Cl3Sm(mu-Cl))(3)SmCl3](3-)[Sm(C6H10O2)(8)](3+), 4与5同晶。 [Cl3Nd(mu-Cl)(3)NdCl3](3-)[Nd(C6H10O2)(8)](3+) 5，从 b = 11.775(4) Angstrom，c = 28.141(5) Angstrom，beta = 96.615(16) 度，V = 6471(3) Angstrom(3) 结晶，并且Z = 4 时的 D 计算值为 1.709 Mg/m(3)。基于 6823 次反射 (\F-0\ > 3.0 sigma(\F-0\)) 的模型最小二乘细化收敛至 R(F) = 5.5%。 [NdCl(mu-Cl)(2)(THF)(2)](n), 6，从二苯甲酮的 THF 溶液中结晶，在空间群 P (1) 中，在棒 [C-i(1) 上； No. 2] 其中 a = 8.2327(13) 埃，b = 8.6177(14) 埃，c = 9.736(2) 埃，alpha = 79.621(13) 度，beta = 70.594(12) 度，gamma = 82.595(13) 度，V = 639.0(2) Angstrom(3)，且 D-calcd = 2.052 Mg/m(3)（Z = 2）。基于 2922 次反射 (\F-0\ > 3.0 sigma(\F-0\)) 的模型最小二乘细化收敛至最终 R(F) = 1.9%。 [CeCl(mu-Cl)2(THF)(2)](n), 7，在空间群 P (1) 中从 L,L-丙交酯的 THF 溶液中结晶，在棒 [C-i(1) 上； No. 2] 其中 a = 8.2558(12) 埃，b = 8.7154(10) 埃，c = 9.7892(12) 埃，α = 79.568(10) 度，beta = 70.580(10) 度，gamma = 82.583(10) 度，V = 651.50(14) Angstrom(3)，D-calcd = 1.991 Mg/m(3)（Z = 2）。基于 1614 次反射 (\F-0\ > 3.0 sigma(\F-0\)) 的模型最小二乘细化收敛至 R(F) = 2.1%。
Crystallization of lanthanide trichlorides from neat epsilon-caprolactone (C6H10O2) and caprolactone/THF mixtures has revealed a much more diverse structural chemistry for solvated lanthanide trichloride complexes than had previously been observed. As the metal is varied, different products preferentially crystallize under the same conditions to give a series of complexes which do not vary smoothly in composition as a function of radial size. The following compounds, in order of increasing radial size of the metal, have been structurally characterized: YbCl3(C6H10O2)(THF)(2), 1; YCl3(C6H10O2)(3), 2; [TbCl4(THF)(2)](-)[TbCl2(THF)(5)](+), 3; [Cl3Sm(mu-Cl)(3)SmCl3](3-)[Sm(C6H10O2)(8)](3+),4; [Cl3Nd(mu-Cl)(3)NdCl3](3-)[Nd(C6H10O2)(8)](3+) 5. In the course of these studies, the polymeric halides [NdCl(mu-Cl)(2)(THF)(2)](n), 6, and [CeCl(mu-Cl)(2)(THF)(2)](n), 7, were also identified by X-ray crystallography. Although both 1 and 2 have octahedral geometries, they differ in the amount of caprolactone present and the fact that 1 is facial while 2 is meridional. The ion pair system 3 contains a six-coordinate anion with a trans octahedral geometry and a seven-coordinate cation with axial chloride ligands in a pentagonal bipyramidal structure. Complexes 4 and 5 contain bimetallic trianions devoid of caprolactone which adopt a face-sharing bioctahedral geometry. The eight-coordinate cations in 4 and 5 contain no chloride ligands and adopt a square antiprismatic geometry. Isostructural 6 and 7 contain seven-coordinate pentagonal bipyramidal metal centers surrounded by four bridging chloride atoms, one terminal chloride, and two terminal THF Ligands. YbCl3(C6H10O2)(THF)(2), 1, crystallized from epsilon-caprolactone/THF in space group P2(1)/n [C-2h(5); No. 14] with a = 11.580(2) Angstrom, b = 12.802(3) Angstrom, c = 13.532(3) Angstrom, beta = 103.462(15)degrees, V = 1951.0(7) Angstrom(3), and D-calcd = 1.831 Mg/m(3) for Z = 4. Least-squares refinement of the model based on 3894 reflections (\F-0\ > 3.0 sigma(\F-0\)) converged to R(F) = 3.5%. YCl3(C6H10O2)(3), 2, crystallized from both epsilon-caprolactone/THF and neat epsilon-caprolactone in the space group P (1) over bar with a = 10.083(1) Angstrom, b = 11.706(1) Angstrom, c = 11.702(1) Angstrom, alpha = 60.071(7)degrees, beta = 81.274(9)degrees, gamma = 75.741(8)degrees, V = 1159.4(2) Angstrom(3), and D-calcd = 1.540 Mg/m(3) for Z = 2. Least-squares refinement of the model based on 4846 observed reflections (\F-0\ > 2.0 sigma(\F-0\)) converged to R(F) = 4.0%. [TbCl4(THF)(2)](-)[TbCl2(THF)(5)](+), 3, crystallized from epsilon-caprolactone/THF in the space group C2/c [C-2h(6),; No. 15] With a = 12.401(2) Angstrom, b = 11.420(2) Angstrom, c = 27.413(3) Angstrom, beta = 91.100(11)degrees, V = 3881.4(9) Angstrom(3), and D-calcd = 1.772 Mg/m(3) for Z = 8. Least-squares refinement of the model based on 3936 reflections (\F-0\ > 3.0 sigma(\F-0\)) converged to R(F) = 3.4%. [Cl3Sm(mu-Cl))(3)SmCl3](3-)[Sm(C6H10O2)(8)](3+), 4, was found to be isomorphous with 5 by a unit cell determination. [Cl3Nd(mu-Cl)(3)NdCl3](3-)[Nd(C6H10O2)(8)](3+) 5, crystallized from b = 11.775(4) Angstrom, c = 28.141(5) Angstrom, beta = 96.615(16)degrees, V = 6471(3) Angstrom(3) and D-calcd 1.709 Mg/m(3) for Z = 4. Least-squares refinement of the model based on 6823 reflections (\F-0\ > 3.0 sigma(\F-0\)) converged to R(F) = 5.5%. [NdCl(mu-Cl)(2)(THF)(2)](n), 6, crystallized from a solution of benzophenone in THF in the space group P (1) over bar [C-i(1); No. 2] with a = 8.2327(13) Angstrom, b = 8.6177(14) Angstrom, c = 9.736(2) Angstrom, alpha = 79.621(13)degrees, beta = 70.594(12)degrees, gamma = 82.595(13)degrees, V = 639.0(2) Angstrom(3), and D-calcd = 2.052 Mg/m(3) for Z = 2. Least-squares refinement of the model based on 2922 reflections (\F-0\ > 3.0 sigma(\F-0\)) converged to a final R(F) = 1.9%. [CeCl(mu-Cl)2(THF)(2)](n), 7, crystallized from a solution of L,L-lactide in THF in the space group P (1) over bar [C-i(1); No. 2] with a = 8.2558(12) Angstrom, b = 8.7154(10) Angstrom, c = 9.7892(12) Angstrom, alpha = 79.568(10)degrees, beta = 70.580(10)degrees, gamma = 82.583(10)degrees, V = 651.50(14) Angstrom(3), and D-calcd = 1.991 Mg/m(3) for Z = 2. Least-squares refinement of the model based on 1614 reflections (\F-0\ > 3.0 sigma(\F-0\)) converged to R(F) = 2.1%.