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The Fascinating Flexibility and Coordination Modes of a Pentamethylene Connected Macrocyclic CNC Pincer Ligand

机译：五亚甲基连接宏环CNC钳子配体的迷人灵活性和配位模式

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摘要

The coordination chemistry of an electron-rich macrocyclic CNC pincer-ligand consisting of two pentamethylene tethered N-heterocyclic carbene moieties on a carbazole backbone (bimcaC5) is investigated by mainly NMR spectroscopy and X-ray crystal structure analysis. A bridging coordination mode is found for the lithium complex. With the larger and softer potassium ion, the ligand adopts a facial coordination mode and a polymeric structure by intermolecular potassium nitrogen interactions. The facial coordination is also confirmed at a Cp*Ru fragment, while C-H activation under dehydrogenation at the alkyl chain is observed upon reaction with [Ru(PPh3)3Cl2]. In contrast, Pd(OAc)2 reacts under C-H activation at the central carbon atom of the pentamethylene tether to an alkyl-pincer macrocycle.

机译：通过主要是NMR光谱和X射线晶体结构分析，研究了由咔唑骨架（BIMCAC5）上的两个五亚甲基系重氮杂环碳切链部分组成的富含电子的大环CNC钳子配体的配位化学。找到锂络合物的桥接协调模式。利用较大且较软的钾离子，配体通过分子间氮相互作用采用面部配位模式和聚合物结构。在CP * Ru片段中也确认面部配位，而在与[Ru（PPH3）3Cl2]反应后观察到烷基链中脱氢的C-H活化。相反，Pd（OAC）2在五亚甲基系重系链状物的C-H溶液中反应至烷基钳宏型。

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期刊名称 Molecules
作者
Ronja Jordan; Doris Kunz;
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作者单位

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年(卷),期 2021(26),6
年度 2021
页码 1669
总页数 12
原文格式 PDF
正文语种
中图分类分子生物学;
关键词
pincer ligand; macrocycle; N-heterocyclic carbene; lithium; potassium; ruthenium; intramolecular C-H activation; dehydrogenation;

机译：钳子配体;宏观;N-杂环卡贝烯;锂;钾;钌;分子内C-H激活;脱氢;

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1. Synthesis of a flexible macrocyclic tetraimidazolium salt-precursor for a tetracarbene ligand with metal dependent coordination modes [J] . Brinke Christian Schulte To, Hahn F. Ekkehardt Dalton transactions: An international journal of inorganic chemistry . 2015,第32期

机译：具有金属依赖性配位方式的四碳烯配体的柔性大环四咪唑鎓盐前体的合成
2. Coordination Polymers Assembled from 3,5-Pyrazoledicarboxytic Acid and Bis(triazolyl) Ligands: Chiral and Meso-Structures Induced by Ligand Flexibility and a Six-Connected Self-Catenated Network [J] . Zhou XH, Du XD, Li GN, Crystal growth & design . 2009,第10期

机译：由3,5-吡唑二甲酸和双（三唑基）配体组装的配位聚合物：配体柔韧性和六连接自连接网络诱导的手性和内消旋结构
3. 2D and 3D cadmium(II) coordination polymers from a flexible tripodal ligand of 1,3,5-tris(carboxymethoxy)benzene and bidentate pyridyl-containing ligands with three-, eight- and ten-connected topologies [J] . Wang SN, Xing H, Li YZ, European journal of inorganic chemistry . 2006,第15期

机译：来自1,3,5-三（羧甲氧基）苯的柔性三脚架配体和具有三连接，八连接和十连接拓扑的含二齿吡啶基的配体的2D和3D镉（II）配位聚合物
4. Cationic Uranium Alkyl Complexes of a Rigid NON-Donor Pincer Ligand: The Impact of Arene-Coordination on Ethylene Polymerization Activity [C] . David J. H. Emslie, N. R. Andreychuk, B. Vidjayacoumar Rare Earth Research Conference . 2019

机译：刚性非供体钳配体的阳离子铀烷基复合物：芳烃配位对乙烯聚合活性的影响
5. The impact of ligand design on the coordination chemistry and reactivity of metal pincer complexes [D] . Wanniarachchi, Sarath 2012

机译：配体设计对金属钳配合物配位化学和反应活性的影响
6. Adapting free energy perturbation simulations for large macrocyclic ligands: how to dissect contributions from direct binding and free ligand flexibility [O] . Kerstin Wallraven, Fredrik L. Holmelin, Adrian Glas, 2020

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7. The Fascinating Flexibility and Coordination Modes of a Pentamethylene Connected Macrocyclic CNC Pincer Ligand [O] . Ronja Jordan, Doris Kunz 2021

机译：五亚甲基连接宏环CNC钳子配体的迷人灵活性和配位模式

The Fascinating Flexibility and Coordination Modes of a Pentamethylene Connected Macrocyclic CNC Pincer Ligand

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