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Synthesis and Characterization of Rare-Earth Metal Complexes Supported by 2-Imino or Amino Appended Indolyl Ligands with Diverse Hapticities: Tunable Selective Catalysis for Isoprene Polymerization
Organometallics ( IF 2.5 ) Pub Date : 2017-09-21 00:00:00 , DOI: 10.1021/acs.organomet.7b00575 Guangchao Zhang 1 , Shaowu Wang 1, 2 , Xiancui Zhu 1 , Shuangliu Zhou 1 , Yun Wei 1 , Zeming Huang 1 , Xiaolong Mu 1
Organometallics ( IF 2.5 ) Pub Date : 2017-09-21 00:00:00 , DOI: 10.1021/acs.organomet.7b00575 Guangchao Zhang 1 , Shaowu Wang 1, 2 , Xiancui Zhu 1 , Shuangliu Zhou 1 , Yun Wei 1 , Zeming Huang 1 , Xiaolong Mu 1
Affiliation
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:
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]。
更新日期:2017-09-21
中文翻译:
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]。