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Rare‐Earth Metal Alkyl Complexes with 3‐Arylamido‐Functionalized Indolyl Ligands: Synthesis, Characterization and Reactivity†
Chinese Journal of Chemistry ( IF 5.5 ) Pub Date : 2020-03-26 , DOI: 10.1002/cjoc.201900555 Xiancui Zhu 1 , Yuzhe Jiang 1 , Jun Chen 1 , Shaowu Wang 1, 2, 3 , Zeming Huang 1 , Shan Zhu 1 , Xu Zhao 2 , Wenrun Yue 1 , Jun Zhang 1 , Weikang Wu 1 , Xiangyang Zhong 1
Chinese Journal of Chemistry ( IF 5.5 ) Pub Date : 2020-03-26 , DOI: 10.1002/cjoc.201900555 Xiancui Zhu 1 , Yuzhe Jiang 1 , Jun Chen 1 , Shaowu Wang 1, 2, 3 , Zeming Huang 1 , Shan Zhu 1 , Xu Zhao 2 , Wenrun Yue 1 , Jun Zhang 1 , Weikang Wu 1 , Xiangyang Zhong 1
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A series of dinuclear rare‐earth metal alkyl complexes {[μ‐η2:η1:η1‐3‐(LNCH)(CH2SiMe3)Ind]RE(CH2SiMe3)(THF)}2 (L1 = 2‐tBuC6H4, RE = Y, Gd, Dy, Er, Yb; L2 = 2,4,6‐Me3C6H2, RE = Dy, Er; Ind = indolyl) and {[μ‐η2:η1:η1‐3‐(LNCH2)Ind]RE(CH2SiMe3)(THF)}2 (L1, RE = Y, Dy, Er, Yb; L2, RE = Er, Yb) bearing 3‐arylamido functionalized indolyl ligands having diverse bonding modes with metal ions were synthesized either by the insertion reaction of the imino group to the RE—C bond or by the alkane elimination reaction. In the preparation of above complexes, rare‐earth metal alkyl complexes [μ‐η5:η1:η1‐3‐(L2NCH)(CH2SiMe3)Ind]Gd(CH2SiMe3)(THF)}2 with a μ‐η5:η1:η1 coordination mode to the gadolinium ion and {[μ‐η3:η1:η1‐3‐(L2NCH2)Ind]Dy(CH2SiMe3)(THF)}2 with a μ‐η3:η1:η1 coordination mode to the dysprosium ion were unexpectedly isolated. The reactions of 3‐(L2N=CH)Ind with Er(CH2SiMe3)3(THF)2 at room temperature, generated a tetranuclear imino‐indolyl erbium intermediate {[μ‐η1:η1‐3‐(L2N=CH)Ind]Er(CH2SiMe3)2(THF)}4, which can transform into the amido functionalized indolyl erbium complex in hot toluene. Moreover, the reactivities of the newly synthesized ytterbium complex with N‐heterocyclic compounds were investigated, affording the corresponding products of the mixed pyridyl‐indolyl, imidazolyl‐indolyl, and ortho‐metalated complexes. The yttrium complexes showed a high regioselectivity and steroselectivity for the isoprene polymerization with 1,4‐trans selectivity up to 91.7% and 1,4‐cis selectivity up to 96.1% in the presence of cocatalysts, respectively.
中文翻译：
具有3-Arylamido功能化的吲哚基配体的稀土金属烷基络合物：合成，表征和反应性†
一系列双核稀土金属的烷基络合物{[ μ-η 2：η 1：η 1 -3-（大号NCH）（CH 2森达3）工业] RE（CH 2森达3）（THF）} 2（L 1 = 2 t BuC 6 H 4，RE = Y，Gd，Dy，Er，Yb；L 2 = 2,4,6-Me 3 C 6 H 2，RE = Dy，Er; Ind =吲哚基）和{[ μ-η 2：η 1：η 1 -3-（L NCH 2）Ind] RE（CH 2 SiMe 3）（THF）} 2（L 1，RE = Y，Dy，Er，Yb; L 2，RE = Er，Yb）带有3-芳酰胺基官能化吲哚基配体通过亚氨基与RE-C键的插入反应或通过烷烃消除反应，可以合成具有金属离子的键合模式。在制备上述络合物，稀土类金属络合物烷基[ μ-η 5：η 1：η 1 -3-（大号2 NCH）（CH 2森达3）工业]钆（CH 2森达3）（THF）} 2与μ - η 5：η 1：η 1配位模式的钆离子和{[ μ-η 3：η 1：η 1 -3-（大号2 NCH 2）工业]的Dy （CH 2森达3）（THF）} 2与μ - η 3：η 1：η 1协调模式向镝离子被意外地分离。3‐（L 2的反应N = CH）工业有Er（CH 2森达3）3（THF）2在室温下，所产生的四核亚氨基吲哚基铒中间体{[ μ - η 1：η 1 -3-（大号2 N = CH）工业] Er（CH 2 SiMe 3）2（THF）} 4，可在热甲苯中转化为酰胺基官能化的吲哚yl络合物。此外，还研究了新合成的complex与N-杂环化合物的反应活性，得到了吡啶基-吲哚基，咪唑基-吲哚基和正交金属配合物。钇配合物在异戊二烯聚合反应中表现出较高的区域选择性和立体选择性，在助催化剂存在下，其1,4-反式选择性高达91.7％，1,4-顺式选择性高达96.1％。
更新日期：2020-04-22
中文翻译：
具有3-Arylamido功能化的吲哚基配体的稀土金属烷基络合物：合成，表征和反应性†
一系列双核稀土金属的烷基络合物{[ μ-η 2：η 1：η 1 -3-（大号NCH）（CH 2森达3）工业] RE（CH 2森达3）（THF）} 2（L 1 = 2 t BuC 6 H 4，RE = Y，Gd，Dy，Er，Yb；L 2 = 2,4,6-Me 3 C 6 H 2，RE = Dy，Er; Ind =吲哚基）和{[ μ-η 2：η 1：η 1 -3-（L NCH 2）Ind] RE（CH 2 SiMe 3）（THF）} 2（L 1，RE = Y，Dy，Er，Yb; L 2，RE = Er，Yb）带有3-芳酰胺基官能化吲哚基配体通过亚氨基与RE-C键的插入反应或通过烷烃消除反应，可以合成具有金属离子的键合模式。在制备上述络合物，稀土类金属络合物烷基[ μ-η 5：η 1：η 1 -3-（大号2 NCH）（CH 2森达3）工业]钆（CH 2森达3）（THF）} 2与μ - η 5：η 1：η 1配位模式的钆离子和{[ μ-η 3：η 1：η 1 -3-（大号2 NCH 2）工业]的Dy （CH 2森达3）（THF）} 2与μ - η 3：η 1：η 1协调模式向镝离子被意外地分离。3‐（L 2的反应N = CH）工业有Er（CH 2森达3）3（THF）2在室温下，所产生的四核亚氨基吲哚基铒中间体{[ μ - η 1：η 1 -3-（大号2 N = CH）工业] Er（CH 2 SiMe 3）2（THF）} 4，可在热甲苯中转化为酰胺基官能化的吲哚yl络合物。此外，还研究了新合成的complex与N-杂环化合物的反应活性，得到了吡啶基-吲哚基，咪唑基-吲哚基和正交金属配合物。钇配合物在异戊二烯聚合反应中表现出较高的区域选择性和立体选择性，在助催化剂存在下，其1,4-反式选择性高达91.7％，1,4-顺式选择性高达96.1％。
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