Functional Group Tolerant Olefin Metathesis Catalysts Based on N-Heterocyclic Carbene Complexes of High Oxidation State Molybdenum Imido Alkylidenes

基于高氧化态亚氨基钼亚烷基N-杂环卡宾配合物的官能团耐受性烯烃复分解催化剂

• 批准号: 271749009
• 负责人: Professor Dr. Michael R. Buchmeiser
• 金额: --
• 依托单位: Lehrstuhl für Makromolekulare Stoffe und Faserchemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/271749009?language=en
• 关键词: Functional; Group; Tolerant; Olefin; Metathesis

N-Heterocyclic carbene (NHC) adducts of high oxidation state Mo-imido alkylidenes shall be prepared. For these purposes, different NHCs, i.e. small, large, strongly basic or nucleophilic ones, shall be used. Variations in catalyst structure shall further comprise of different anionic ligands such as alkoxides, phenoxides, carboxylates, iso(thio)cyanates as well as of different imido-ligands. The chosen approach will allow elucidating the activating effect of the NHC on the metal alkylidene in terms of ligand dissociation and concomitant formation of cationic alkylidene species. Furthermore, the role of the anionic ligands will be elucidated. Notable, metal complexes with mixed anionic ligands are accessible. In terms of different types of metathesis reactions for which the novel systems shall be used, we wish to address olefin metathesis reactions relevant to both organic synthesis and polymer chemistry. These will comprise of ring-closing metathesis (RCM), cross-metathesis (CM), ring-opening cross metathesis (ROCM) enyne / ene-diyne metathesis and self-metathesis (SM) reactions as well as of ring-opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) polymerization and the cyclopolymerization of diynes. With ionic catalysts, all the envisaged reaction types including polymerization reactions can be carried out under biphasic conditions. With the exception of cyclopolymerization, continuous supported ionic liquid phase (SILP) conditions can be applied. In CM, enyne and SM reactions, but also in ROMP and cyclopolymerization, special attention will be devoted to stereoselectivity. The proposed work will not only broaden the understanding about high oxidation state metal alkylidene NHC complexes, but also offer a new class of functional group tolerant, highly active stereo- and regioselective catalysts for olefin metathesis-based C-C coupling reactions.

应制备高氧化态MO-IMIDO烷基丙烯的N-杂环碳（NHC）加合物。为了这些目的，应使用不同的NHC，即小型，大，强大或亲核的。催化剂结构的变化应进一步包括不同的阴离子配体，例如烷氧化物，苯氧化物，羧酸盐，ISO（硫代）氰化物以及不同的imido-凸层。所选方法将允许在配体解离和阳离子烷基丙烯物种的配体解离和伴随形成方面阐明NHC对金属烷基丙烯的激活作用。此外，将阐明阴离子配体的作用。值得注意的是，可访问带有混合阴离子配体的金属络合物。就应使用新型系统的不同类型的元理解反应而言，我们希望解决与有机合成和聚合物化学相关的烯烃元理解反应。 These will comprise of ring-closing metathesis (RCM), cross-metathesis (CM), ring-opening cross metathesis (ROCM) enyne / ene-diyne metathesis and self-metathesis (SM) reactions as well as of ring-opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) polymerization and the cyclopolymerization of diynes.使用离子催化剂，可以在双相条件下进行所有设想的反应类型，包括聚合反应。除环聚合外，连续支持的离子液相（SILP）条件可以应用。在CM，Enyne和SM反应中，以及在romp和cycloperalization中，特别关注的是立体选择性。拟议的工作不仅将扩大对高氧化状态金属烷基烷基NHC复合物的理解，而且还提供了一类新的功能组耐受性，高度活性的立体和区域选择性催化剂，用于基于烯烃的C-C偶联反应。

项目成果

Stereoselective Ring-Opening Metathesis Polymerization with Molybdenum Imido Alkylidenes Containing O-Chelating N-Heterocyclic Carbenes: Influence of Syn/Anti Interconversion and Polymerization Rates on Polymer Structure

• DOI: 10.1021/acs.macromol.7b00841
• 发表时间: 2017-08-08
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Lienert, Christina;Frey, Wolfgang;Buchmeiser, Michael R.
• 通讯作者: Buchmeiser, Michael R.

Latent and Air-Stable Pre-Catalysts for the Polymerization of Dicyclopentadiene: From Penta- to Hexacoordination in Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes.

• DOI: 10.1002/chem.201801862
• 发表时间: 2018-07
• 期刊: Chemistry
• 作者: Iris Elser;Benjamin R. Kordes;W. Frey;Katharina Herz;Roman Schowner;L. Stöhr;H. -. Altmann;M. Buchmeiser

Neutral and Cationic Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes: Reactivity in Selected Olefin Metathesis Reactions and Immobilization on Silica.

中性和阳离子钼亚氨基亚烷基 N-杂环卡宾配合物：选定的烯烃复分解反应中的反应性和二氧化硅上的固定化

• DOI: 10.1002/chem.201501615
• 发表时间: 2015
• 期刊: Chemistry
• 作者: S. Sen;R. Schowner;D. A. Imbrich;W. Frey;M. R. Buchmeiser
• 通讯作者: M. R. Buchmeiser