Ionic Pd/NHC Catalytic System Enables Recoverable Homogeneous Catalysis: Mechanistic Study and Application in the Mizoroki–Heck Reaction

Dmitry B. Eremin; Ekaterina A. Denisova; Alexander Yu. Kostyukovich; Jonathan Martens; Giel Berden; Jos Oomens; Victor N. Khrustalev; Victor M. Chernyshev; Valentine P. Ananikov

首页> 外文期刊>Chemistry: A European journal >Ionic Pd/NHC Catalytic System Enables Recoverable Homogeneous Catalysis: Mechanistic Study and Application in the Mizoroki–Heck Reaction

【24h】

Ionic Pd/NHC Catalytic System Enables Recoverable Homogeneous Catalysis: Mechanistic Study and Application in the Mizoroki–Heck Reaction

机译：离子Pd / NHC催化系统使可收回的均匀催化：机械研究和在Mizoroki-Heck反应中的应用

获取原文

获取原文并翻译 | 示例

掌桥外文数据库（机构版） >>

开具论文收录证明 >>

文献代查 >>

页面导航

摘要
著录项
相似文献
相关主题

摘要

N-Heterocyclic carbene (NHC) ligands are ubiquitously utilized in catalysis. A common catalyst design model assumes strong M–NHC binding in this metal–ligand framework. In contrast to this common assumption, we demonstrate here that lability and controlled cleavage of the M@ NHC bond (rather than its stabilization) could be more important for high-performance catalysis at low catalyst concentrations. The present study reveals a dynamic stabilization mechanism with labile metal–NHC binding and [PdX_3]@[NHC-R]~+ ion pair formation. Access to reactive anionic palladium intermediates formed by dissociation of the NHC ligands and plausible stabilization of the molecular catalyst in solution by interaction with the [NHC-R]~+ azolium ion is of particular importance for an efficient and recyclable catalyst. These ionic Pd/NHC complexes allowed for the first time the recycling of the complex in a well-defined form with isolation at each cycle. Computational investigation of the reaction mechanism confirms a facile formation of NHCfree anionic Pd in polar media through either Ph–NHC coupling or reversible H–NHC coupling. The present study formulates novel ideas for M/NHC catalyst design.

机译：N-杂环基石（NHC）配体在催化中普遍存在。常见的催化剂设计模型假设该金属配体框架中的强M-NHC结合。与这种常见的假设相比，我们证明了M @ NHC键（而不是其稳定化）的可怜和受控切割可能对低催化剂浓度的高性能催化更重要。本研究揭示了具有不稳定金属-NHC结合的动态稳定机理和[PDX_3] @ [NHC-R]〜+离子对形成。通过与[NHC-R]〜乙醇离子相互作用的溶液中的NHC配体的解离和分子催化剂的可合理稳定性的进入通过与[NHC-R]〜+氮杂离子相互作用，对高效和可回收的催化剂特别重要。这些离子Pd / NHC复合物首次允许在每个循环中以明确定义的形式再循环复合物。反应机制的计算研究证实了通过PH-NHC偶联或可逆的H-NHC耦合来在极性培养基中形成NHCFREE阴离子Pd的容貌形成。本研究制定了M / NHC催化剂设计的新思想。

著录项

来源
《Chemistry: A European journal》 |2019年第72期|共9页
作者
Dmitry B. Eremin; Ekaterina A. Denisova; Alexander Yu. Kostyukovich; Jonathan Martens; Giel Berden; Jos Oomens; Victor N. Khrustalev; Victor M. Chernyshev; Valentine P. Ananikov;
展开▼
作者单位

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Pr. 47 Moscow 119991 (Russia);

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Pr. 47 Moscow 119991 (Russia);

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Pr. 47 Moscow 119991 (Russia);

Institute for Molecules and Materials FELIX Laboratory Radboud University Toernooiveld 7c 6525 ED Nijmegen (The Netherlands);

Institute for Molecules and Materials FELIX Laboratory Radboud University Toernooiveld 7c 6525 ED Nijmegen (The Netherlands);

Institute for Molecules and Materials FELIX Laboratory Radboud University Toernooiveld 7c 6525 ED Nijmegen (The Netherlands);

National Research Center ?Kurchatov Institute? Acad. Kurchatov Sq. 1 Moscow 123182 (Russia);

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Pr. 47 Moscow 119991 (Russia);

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Pr. 47 Moscow 119991 (Russia);

展开▼
收录信息
原文格式 PDF
正文语种 eng
中图分类应用化学;
关键词
carbene ligands; dynamic catalysis; electrospray ionization; mass spectrometry; Mizoroki–Heck reaction;

机译：卡宾配体;动态催化;电喷雾电离;质谱;Mizoroki-Heck反应;

相似文献

外文文献
中文文献
专利

1. Ionic Pd/NHC Catalytic System Enables Recoverable Homogeneous Catalysis: Mechanistic Study and Application in the Mizoroki–Heck Reaction [J] . Dmitry B. Eremin, Ekaterina A. Denisova, Alexander Yu. Kostyukovich, Chemistry: A European journal . 2019,第72期

机译：离子Pd / NHC催化系统使可收回的均匀催化：机械研究和在Mizoroki-Heck反应中的应用
2. A nano tetraimine Pd(0) complex: synthesis, characterization, computational studies and catalytic applications in the Heck-Mizoroki reaction in water [J] . Mandegani Zeinab, Asadi Mozaffar, Asadi Zahra, Green chemistry . 2015,第6期

机译：纳米四亚胺Pd（0）配合物：水中Heck-Mizoroki反应的合成，表征，计算研究和催化应用
3. Mechanistic investigation of Heck reaction catalyzed by new catalytic system composed of Fe3O4@OA-Pd and ionic liquids as co-catalyst [J] . Rafiee Ezzat, Kahrizi Masoud Journal of Molecular Liquids . 2016,第Null期

机译：Fe3O4 @ OA-Pd和离子液体为助催化剂组成的新型催化体系催化的Heck反应机理
4. Rapid and Diversity-Oriented Construction of Extended n-Electron Systems Using Double Mizoroki-Heck Reaction and Double Hiyama Cross-Coupling Reaction [C] . Kenichiro Itami, Yoichi Ohashi, Toshiki Nokami, Symposium on Organometallic Chemistry . 2003

机译：使用双米兹多洛 - Heck反应和双重山上交叉偶联反应的快速和多样化延伸N型电子系统的建设
5. Effort Towards an Intermolecular Reductive-Heck Reaction with Homogeneous and Heterogeneous Palladium Catalysis [D] . Rosas Vargas, Daisy. 2019

机译：与均相和异质钯催化分子间还原的努力
6. An efficient Pd–NHC catalyst system in situ generated from Na2PdCl4 and PEG-functionalized imidazolium salts for Mizoroki–Heck reactions in water [O] . Nan Sun, Meng Chen, Liqun Jin, 2017

机译：由Na2PdCl4和PEG官能化的咪唑鎓盐原位生成的高效Pd-NHC催化剂体系用于水中的Mizoroki-Heck反应
7. An efficient Pd–NHC catalyst system in situ generated from Na₂PdCl₄ and PEG-functionalized imidazolium salts for Mizoroki–Heck reactions in water [O] . Nan Sun, Meng Chen, Liqun Jin, 2017

机译：由Na _{2 pdCl _{4 和pEG官能化的咪唑鎓盐原位生成的有效pd-NHC催化剂体系，用于水中的mizoroki-Heck反应}}

Ionic Pd/NHC Catalytic System Enables Recoverable Homogeneous Catalysis: Mechanistic Study and Application in the Mizoroki–Heck Reaction

摘要

著录项

相似文献

相关主题

期刊订阅