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

基本信息

项目摘要

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

期刊论文数量(5)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
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:
  • 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:
  • 影响因子:
    0
  • 作者:
    Iris Elser;Benjamin R. Kordes;W. Frey;Katharina Herz;Roman Schowner;L. Stöhr;H. -. Altmann;M. Buchmeiser
  • 通讯作者:
    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:
  • 影响因子:
    0
  • 作者:
    S. Sen;R. Schowner;D. A. Imbrich;W. Frey;M. R. Buchmeiser
  • 通讯作者:
    M. R. Buchmeiser
共 3 条
  • 1
前往

Professor Dr. Mich...的其他基金

High Oxidation State Tungsten Oxo, Tungsten Thio, and Tungsten Imido Alkylidene NHC Complexes for Olefin Metathesis of Functional Olefins
高氧化态氧化钨、硫代钨和亚氨基亚烷基钨 NHC 配合物用于功能性烯烃的烯烃复分解
  • 批准号:
    319116190
    319116190
  • 财政年份:
    2016
  • 资助金额:
    --
    --
  • 项目类别:
    Research Grants
    Research Grants
High Modulus and High Strength C/C-SiC Ceramic Matrix Composites by Fiber-Matrix Interface Tailoring via Modification of Fiber Surface and Matrix Precursor - Kerafam 2
通过纤维表面和基体前驱体改性实现纤维基体界面定制的高模量和高强度 C/C-SiC 陶瓷基复合材料 - Kerafam 2
  • 批准号:
    277680365
    277680365
  • 财政年份:
    2015
  • 资助金额:
    --
    --
  • 项目类别:
    Research Grants
    Research Grants
Polymerization Catalysts for the Reversible Switching Between Vinyl Insertion and Ring-Opening Metathesis Polymerization
用于乙烯基插入和开环复分解聚合之间可逆转换的聚合催化剂
  • 批准号:
    226688656
    226688656
  • 财政年份:
    2012
  • 资助金额:
    --
    --
  • 项目类别:
    Research Grants
    Research Grants
Metathesis under Biphasic Conditions Using Monolithic-Supported Ionic Liquids
使用整体支撑离子液体在双相条件下进行复分解
  • 批准号:
    136355964
    136355964
  • 财政年份:
    2010
  • 资助金额:
    --
    --
  • 项目类别:
    Research Grants
    Research Grants
Regio- and Stereoselective Cyclopolymerization of Functional 1,6-Heptadiynes and 1,5-Hexadiynes: Rationalizing Catalyst Activity with Monomer Structure
功能性 1,6-庚二炔和 1,5-己二炔的区域和立体选择性环聚合:通过单体结构合理化催化剂活性
  • 批准号:
    41694162
    41694162
  • 财政年份:
    2007
  • 资助金额:
    --
    --
  • 项目类别:
    Research Grants
    Research Grants
Novel photoactive transition metal catalysts for the UV-Light-Triggered Metathesis Polymerization of Functional Monomers
用于紫外光触发功能单体复分解聚合的新型光活性过渡金属催化剂
  • 批准号:
    25106151
    25106151
  • 财政年份:
    2006
  • 资助金额:
    --
    --
  • 项目类别:
    Research Grants
    Research Grants
Monolithisch-geträgerte Metall-Nanocluster für katalytische Anwendungen
用于催化应用的整体支撑金属纳米团簇
  • 批准号:
    20805014
    20805014
  • 财政年份:
    2006
  • 资助金额:
    --
    --
  • 项目类别:
    Research Grants
    Research Grants
Origin of Differences in Regioselectivity in the (Cyclo-) Polymerization of alpha, omega-Diynes and 1-Alkynes Between Tetra- and Penta-Coordinated Mo/W Imido/Oxo Alkylidene N-Heterocyclic Carbene Complexes and Implications for Ene-yne Metathesis
四配位和五配位Mo/W亚氨基/氧代亚烷基N-杂环卡宾配合物之间α、omega-二炔和1-炔烃的(环)聚合中区域选择性差异的起源及其对烯-炔复分解的影响
  • 批准号:
    449377332
    449377332
  • 财政年份:
  • 资助金额:
    --
    --
  • 项目类别:
    Research Grants
    Research Grants

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