Reactivity of 3-Imino-Functionalized Indoles with Rare-Earth-Metal Amides: Unexpected Substituent Effects on C-H Activation Pathways and Assembly of Rare-Earth-Metal Complexes
Reactivity of 3-Imino-Functionalized Indoles with Rare-Earth-Metal Amides: Unexpected Substituent Effects on C-H Activation Pathways and Assembly of Rare-Earth-Metal Complexes
复制标题
3-亚氨基官能化吲哚与稀土金属酰胺的反应性：取代基对 C-H 激活途径和稀土金属配合物组装的意外影响
DOI：
10.1021/acs.organomet.6b00221
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发表时间：
2016
期刊：
影响因子：
2.8
通讯作者：
Zhang Lijun
中科院分区：
文献类型：
--
作者：
Zhu Xiancui;Li Yang;Wei Yun;Wang Shaowu;Zhou Shuangliu;Zhang Lijun
研究了不同3-亚氨基取代吲哚与稀土金属酰胺[（Me 3Si）2N]3RE（μ-Cl）Li（THF）3的反应，发现取代基对C-H键活化途径的影响，导致稀土金属配合物的形成. 3-（叔丁基亚氨基）吲哚与[（Me 3Si）2N]3RE（μ-Cl）Li（THF）3反应，生成了四核稀土金属配合物{[η1：（μ2-η1：η1）：η1-3-（tBuN CH）C8 H4 N] RE 2（μ2-Cl）2（THF）[N（SiMe 3）2]（η1：η1-[μ-η5：η2-3-（tBuN CH）C8 H5 N]2Li）}2（RE = Ho（1a），Er（1b）），其中含有独特的吲哚基1，2-二价阴离子，通过sp 2C-H活化，以η1：（μ2-η1：η1）模式与中心金属键合. 3-（苯基亚氨基）吲哚与[（Me 3Si）2N]3RE（μ-Cl）Li（THF）3反应，通过sp 3C-H键的活化和C-C键的偶联反应，得到了新的双核配合物{3-[PhNCH（CH 2SiMe 2）N（SiMe 3）] C8 H5 NRE（THF）（μ2-Cl）Li（THF）2}2（RE = Y（2a），Sm（2b），Dy（2c），Yb（2d））.治疗3-（2-甲基苯基亚氨基）吲哚或3-（2-甲基苯基亚氨基）吲哚。[（Me_3Si）_2N]_3Yb（μ-Cl）Li（THF）_3与4-甲基苯亚氨基吲哚反应生成相应的双核稀土金属氨基配合物{3-[（2-MePh）NCH（CH 2SiMe 2）N（SiMe 3）] C8 H5 NYb（THF）（μ2-Cl）Li（THF）2}2（3）和{3-[（4-MePh）NCH（CH 2SiMe 2）N（SiMe 3）] C8 H5 NYb（THF）（μ2-Cl）Li（THF）2}2（4），遵循与形成配合物2a-d相同的途径。3-（4-叔丁基苯基亚氨基）吲哚与[（Me 3Si）2N]3RE（μ-Cl）Li（THF）3反应，通过sp 3C-H键活化和C-C键偶联反应，得到了新的六核稀土金属配合物{3-[（4-tBu-Ph）NHCH（CH 2SiMe 2）N（SiMe 3）] C8 H5 NREN（SiMe 3）2}6（RE = Dy（5a），Ho（5 b），Er（5c））.相反，在与5的制备条件相同的条件下，与相应的钇络合物反应得到新的杂六钇络合物{3-[（4-tBu-Ph）NCH（CH 2SiMe 2）N（SiMe 3）] C8 H 5 NYN（SiMe 3）2Li（THF）}6（6），其具有4-tBu-anilido部分。通过元素分析、光谱分析和X-射线结构分析对所有配合物进行了表征。这些不同的稀土金属配合物的形成提出了合理的途径。
The reactivities of different 3-imino-functionalized indoles with rare-earth-metal amides [(Me3Si)2N]3RE(μ-Cl)Li(THF)3were studied to reveal unexpected substituent effects on C–H bond activation pathways, leading to the formation of unusual rare-earth-metal complexes. The reactions of 3-(tert-butylimino)indole with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3produced tetranuclear rare-earth-metal complexes {[η1:(μ2-η1:η1):η1-3-(tBuNCH)C8H4N]RE2(μ2-Cl)2(THF)[N(SiMe3)2](η1:η1-[μ-η5:η2-3-(tBuNCH)C8H5N]2Li)}2(RE = Ho (1a), Er (1b)), incorporating a unique indolyl-1,2-dianion through sp2C–H activation bonded with the central metal in η1:(μ2-η1:η1) mode. The reactions of 3-(phenylimino)indole with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3afforded novel binuclear complexes formulated as {3-[PhNCH(CH2SiMe2)N(SiMe3)]C8H5NRE(THF)(μ2-Cl)Li(THF)2}2(RE = Y (2a), Sm (2b), Dy (2c), Yb (2d)) through an unexpected sp3C–H bond activation with subsequent C–C bond coupling reactions. Treatment of 3-(2-methylphenylimino)indole or 3-(4-methylphenylimino)indole with [(Me3Si)2N]3Yb(μ-Cl)Li(THF)3generated the corresponding dinuclear rare-earth-metal amido complexes {3-[(2-MePh)NCH(CH2SiMe2)N(SiMe3)]C8H5NYb(THF)(μ2-Cl)Li(THF)2}2(3) and {3-[(4-MePh)NCH(CH2SiMe2)N(SiMe3)]C8H5NYb(THF)(μ2-Cl)Li(THF)2}2(4), following the same pathway for the formation of complexes2a–d. Treatment of 3-(4-tert-butylphenylimino)indole with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3afforded new hexanuclear rare-earth-metal complexes {3-[(4-tBu-Ph)NHCH(CH2SiMe2)N(SiMe3)]C8H5NREN(SiMe3)2}6(RE = Dy (5a), Ho (5b), Er (5c)) via sp3C–H bond activation followed by C–C bond coupling reactions. In contrast, under the same conditions as those for the preparation of5, the reaction with the corresponding yttrium complex provided the new heterohexayttrium complex {3-[(4-tBu-Ph)NCH(CH2SiMe2)N(SiMe3)]C8H5NYN(SiMe3)2Li(THF)}6(6), having a 4-tBu-anilido moiety. All of these complexes were fully characterized by elemental analysis, spectroscopic methods, and X-ray structure analysis. Plausible pathways for the formation of these different rare-earth-metal complexes were proposed.