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.

制备高氧化态mo -亚胺烷基烷的n -杂环碳（NHC）加合物。为了这些目的，不同的NHCs，即小的、大的、强碱性的或亲核的，应使用。催化剂结构的变化应进一步包括不同的阴离子配体，如烷氧化物、苯氧化物、羧酸盐、异（硫）氰酸盐以及不同的氨基配体。所选择的方法将允许阐明NHC在配体解离和伴随形成的阳离子烷基烷物种方面对金属烷基烷的激活作用。此外，阴离子配体的作用将被阐明。值得注意的是，混合阴离子配体的金属配合物是可接近的。在不同类型的转化反应方面，我们希望解决与有机合成和聚合物化学相关的烯烃转化反应。这些反应将包括闭环复分解（RCM）、交叉复分解（CM）、开环交叉复分解（ROCM）炔/烯-二炔复分解和自复分解（SM）反应，以及开环复分解聚合（ROMP）、无环二烯复分解（ADMET）聚合和双炔的环聚合。使用离子催化剂，包括聚合反应在内的所有预期反应类型都可以在双相条件下进行。除环聚合外，可采用连续负载离子液相（SILP）条件。在CM，炔和SM反应中，以及在ROMP和环聚合中，将特别关注立体选择性。该研究不仅拓宽了人们对高氧化态金属烷基烷NHC配合物的认识，而且为烯烃合成的C-C偶联反应提供了一类新的官能团耐受性强、高活性的立体选择性和区域选择性催化剂。

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