The reaction of 2-(2,6-DippNHCH₂)C₈H₅NH (Dipp = 2,6-ⁱPrC₆H₃, C₈H₅NH = indolyl) with 1 equiv of (Me₃SiCH₂)₃Yb(THF)₂ at room temperature generated mononuclear ytterbium complex 1 having the indolyl ligands in η¹:η¹ mode with reduction of Yb³⁺ to Yb²⁺ and oxidation of the amino to imino group. In the case of Er and Y, the reactions produced dinuclear complexes 2 and 3 having the indolyl ligands in μ-η²:η²:η¹ modes with the central metals. When the rare-earth metal is dysprosium, the reaction afforded mixed ligated dinuclear complex 4a having indolyl ligands in μ-η⁵:η¹:η¹ and μ-η⁶:η¹:η¹ modes with Dy, and its isomer 4b having the indolyl ligands only in μ-η⁵:η¹:η¹ modes with Dy. However, when the rare-earth metal is Gd, the reaction only produced the mixed ligated dinuclear gadolinium complex [(μ-η⁵:η¹:η¹)-2-(2,6-DippNCH₂)Ind(μ-η⁶:η¹:η¹)-2-(2,6-DippNCH₂)Ind][Gd(CH₂SiMe₃)(thf)]₂ (5), having indolyl ligands in μ-η⁵:η¹:η¹ and μ-η⁶:η¹:η¹ modes with Gd. In addition, treatment of 2-(2,6-DippNHCH₂)C₈H₅NH with 1.25 equiv of (Me₃SiCH₂)₃Gd(THF)₂ produced the alkoxido-bridged trinuclear gadolinium complex [(μ-η³:η²:η¹:η¹)-2-(2,6-DippNCH₂)Ind(μ-η²:η¹:η¹)-2-(2,6-DippNCH₂)Ind-(η¹:η¹)-2-(2,6-DippNCH₂)Ind]-Gd₃[(μ₃-O(CH₂)₅SiMe₃)(μ₂-O(CH₂)₅SiMe₃)(thf)₃] (6) having indolyl ligands in η¹:η¹, μ-η²:η¹:η¹, and μ-η³:η²:η¹:η ¹ modes with metals, respectively. In complex 6, sp² C–H activation is observed at the 7-indolyl position producing unique 2-amido substituted indolyl-1,7-dianions having a μ-η³:η²:η¹:η¹ bonding modes with three metals. The O(CH₂)₅SiMe₃ arises from the ring-opening of THF by attack of CH₂SiMe₃. Moreover, when 2-(2,6-DippNHCH₂)C₈H₅NH was treated with 1 equiv of (Me₃SiCH₂)₃Sm(THF)₂, a dinuclear samarium complex [μ-η³:η¹:η¹-2-(2,6-DippNCH₂)Ind]₃Sm₂(thf)₃ (7) having a bridged indolyl ligand in μ-η³:η¹:η¹ hapticities was isolated. All structures of the complexes have been determined by X-ray crystallographic analyses. Dinuclear alkyl complexes 2–5 have been tested as isoprene polymerization initiators in the presence of AlⁱBu₃ and [Ph₃C][B(C₆F₅)₄]. The regioselectivity for isoprene polymerization is tunable from 1,4-cis (up to 93.5%) to 3,4- (up to 86.2%) selectivity by these catalysts simply by adjusting the addition order of AlⁱBu₃ and [Ph₃C][B(C₆F₅)₄].

中文翻译：

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具有不同触觉的2-氨基或氨基附加的吲哚基配体支持的稀土金属配合物的合成和表征：异戊二烯聚合反应的可调选择性催化

2-（2,6- DippNHCH的反应₂）C ₈ H ^ ₅ NH（迪普= 2,6-^我PRC ₆ ħ ₃，C ₈ H ^ ₅ NH =吲哚基）与1个当量的（ME ₃ SICH ₂）₃镱（THF）₂在室温下产生的单核镱复杂1具有在η的吲哚基配体¹：η ¹模式与还原的Yb ³⁺到的Yb ²⁺和氧化氨基的对亚氨基。在Er和Y的情况下，反应生成双核配合物2和3具有吲哚基配体在μ-η ²：η ²：η ^1种模式与中心金属。当稀土类金属是镝，反应得到的混合连接的双核配合物4a中具有吲哚基配体在μ-η ⁵：η ¹：η ¹和μ-η ⁶：η ¹：η ^1种模式与Dy和其异构体4b中仅具有在μ-η吲哚基配体⁵：η ¹：η ^1种模式与镝。然而，当稀土类金属为Gd，只有所产生的混合连接的双核钆络合物[（μ-η反应⁵：η¹：η ¹）-2-（2,6- DippNCH ₂）工业（μ-η ⁶：η ¹：η ¹）-2-（2,6- DippNCH ₂）工业] [钆（CH ₂森达₃） （THF）] ₂（5）中，具有吲哚基配体在μ-η ⁵：η ¹：η ¹和μ-η ⁶：η ¹：η ^1种模式以Gd。另外，用1.25当量的（Me ₃ SiCH ₂）₃ Gd（THF）₂处理2-（2,6-DippNHCH ₂）C ₈ H ₅ NH产生的alkoxido-桥联三核钆配合物[（μ-η ³：η ²：η ¹：η ¹）-2-（2,6- DippNCH ₂）工业（μ-η ²：η ¹：η ¹）-2 - （2,6-二DippNCH ₂）工业-（η ¹：η ¹）-2-（2,6- DippNCH ₂）工业] -Gd ₃ [（μ ₃ - O（CH ₂）₅森达₃）（μ ₂ -O（CH ₂）₅ SiMe ₃）（thf）₃ ]（6），具有吲哚基配体在η ¹：η ¹，μ-η ²：η ¹：η ¹，μ-η ³：η ²：η ¹：η ^1种分别模式与金属，。在复杂6，SP ² C-H活化是在7-吲哚基位置所观察到产生独特2-酰氨基取代的具有μ-η吲哚基-1,7-二价阴离子³：η ²：η ¹：η ¹键合模式可具有三个金属。O（CH ₂）₅ SiMe ₃是由于CH ₂的侵蚀导致THF开环而产生的SiMe ₃。此外，当2-（2,6- DippNHCH ₂）C ₈ H ^ ₅ NH用1个当量的处理（ME ₃ SICH ₂）₃的Sm（THF）₂，双核钐络合物[μ-η ³：η ¹： η ¹ -2-（2,6- DippNCH ₂）工业] ₃的Sm ₂（THF）₃（7），其具有桥联吲哚基配体在μ-η ³：η ¹：η ¹触觉是孤立的。配合物的所有结构均已通过X射线晶体学分析确定。双核配合物烷基2 - 5已测试如在Al的存在异戊二烯聚合引发剂^我卜₃和[PH ₃ C] [B（C ₆ ˚F ₅）₄ ]。只需调整Al ⁱ Bu ₃和[Ph ₃ C]的添加顺序，这些催化剂的异戊二烯聚合反应的区域选择性就可以从1,4-顺式（最高93.5％）调节到3,4-顺式（最高86.2％）选择性。] [B（C ₆ F ₅）₄]。