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
基本信息
- 批准号:319116190
- 负责人:
- 金额:--
- 依托单位:
- 依托单位国家:德国
- 项目类别:Research Grants
- 财政年份:2016
- 资助国家:德国
- 起止时间:2015-12-31 至 2019-12-31
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
Both neutral and cationic high-oxidation state tungsten oxo, tungsten thio and tungsten imido alkylidene N-heterocyclic carbene (NHC) complexes of the general formula W(E)(CHCMe2R)(NHC)X2 and [W(E)(CHCMe2R)(NHC)X+ Y-] (E = O, S, NR1; R1 = tBu, Ad, Ar; R = CH3, Ph) shall be prepared. Besides of the substitution of oxygen by S and NR1, the use of different NHCs with substantially different sigma-donor capability shall be investigated. Variations shall include but not be limited to NHC = imidazol-2-ylidenes, imidazolidin-2-ylidenes, cyclic alkyl aminocarbenes (CAACs), cyclic (amino)(aryl)carbenes (CAArCs), tetrazolin-2-ylidenes, pyrazolin-4-ylidenes, triazol-2-ylidenes and R6-carbodiphosphoranes (R = alkyl, phenyl). In terms of the anionic X-ligand, both weak and stronger sigma-donor ligands such as (fluorinated) alkoxides, thiolates, thiophenolates and iodide shall be used. This will allow identifying the influence of the E-, NHC- and the X-ligand on both the reactivity and functional group tolerance in various olefin metathesis reactions. These will comprise of ring-closing metathesis (RCM), homo-metathesis, cross-metathesis (CM), self-metathesis (SM), ring-opening cross-metathesis (ROCM) and ene-diyne metathesis reactions as well as of ring-opening metathesis polymerization (ROMP). In HM, SM, CM, ene-diyne and ROCM reactions, but also in ROMP, special attention will be devoted to stereoselectivity, an issue that shall be addressed with the aid of novel ansa-type NHCs and NHCs with different sigma-donor capability. In particular, the issue of Z-selectivity shall be addressed and the structure (TB vs. SP) of the tungstacyclobutane shall be elucidated. The work proposed here is not only intended to broaden the understanding about tungsten oxo/thio/imido alkylidene NHC complexes, but also to offer a new class of functional group tolerant, highly active, stereo- and regioselective catalysts for olefin metathesis-based C-C coupling reactions. Last but not least, we will apply the elaborated concept to the synthesis of highly stereoregular polymers via ROMP.
应制备通式为W(E)(CHCMe 2 R)(NHC)X2和[W(E)(CHCMe 2 R)(NHC)X+ Y-](E = O、S、NR 1; R1 = tBu、Ad、Ar; R = CH 3、Ph)的中性和阳离子高氧化态钨氧代、钨硫代和钨亚氨基烷叉N-杂环卡宾(NHC)络合物。除了用S和NR 1取代氧之外,还应研究使用具有显著不同的σ供体能力的不同NHC。变体应包括但不限于NHC =咪唑-2-亚基、咪唑烷-2-亚基、环烷基氨基卡宾(CAAC)、环(氨基)(芳基)卡宾(CAArC)、四唑啉-2-亚基、吡唑啉-4-亚基、三唑-2-亚基和R6-正膦(R =烷基、苯基)。就阴离子X-配体而言,应使用弱和强σ-供体配体,例如(氟化)醇盐、硫醇盐、硫酚盐和碘化物。这将允许鉴定E-、NHC-和X-配体对各种烯烃复分解反应中的反应性和官能团耐受性的影响。这些将包括闭环复分解(RCM)、同易位、交叉复分解(CM)、自复分解(SM)、开环交叉复分解(ROCM)和烯-二炔复分解反应以及开环复分解聚合(ROMP)。在HM、SM、CM、烯-二炔和ROCM反应中,以及在ROMP中,将特别关注立体选择性,这是一个应借助于新型柄型NHC和具有不同σ供体能力的NHC来解决的问题。特别是,Z-选择性的问题将得到解决,并应阐明钨环丁烷的结构(TB与SP)。本文的工作不仅拓宽了对钨氧代/硫代/亚氨基亚烷基NHC配合物的认识,而且为烯烃复分解C-C偶联反应提供了一类新的官能团耐受性、高活性、立体选择性和区域选择性的催化剂。最后但并非最不重要的是,我们将应用精心设计的概念,通过开环易位聚合物的高度有规立构的聚合物的合成。
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)
Synthesis of trans-Isotactic Poly(norbornene)s through Living Ring-Opening Metathesis Polymerization Initiated by Group VI Imido Alkylidene N-Heterocyclic Carbene Complexes
- DOI:10.1021/acs.macromol.9b00422
- 发表时间:2019-06-11
- 期刊:
- 影响因子:5.5
- 作者:Benedikter, Mathis J.;Schowner, Roman;Buchmeiser, Michael R.
- 通讯作者:Buchmeiser, Michael R.
Reversible N‐Heterocyclic Carbene‐Induced α‐H Abstraction in Tungsten(VI) Imido Dialkyl Dialkoxide Complexes
钨 (VI) 亚氨基二烷基二烷氧基配合物中可逆 Nâ杂环卡宾â诱导的 αH 抽象
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:J. V. Musso;M. J. Benedikter;D. Wang;W. Frey;H. J. Altmann;M. R. Buchmeiser
- 通讯作者:M. R. Buchmeiser
{{
item.title }}
{{ item.translation_title }}
- DOI:
{{ item.doi }} - 发表时间:
{{ item.publish_year }} - 期刊:
- 影响因子:{{ item.factor }}
- 作者:
{{ item.authors }} - 通讯作者:
{{ item.author }}
数据更新时间:{{ journalArticles.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ monograph.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ sciAawards.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ conferencePapers.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ patent.updateTime }}
Professor Dr. Michael R. Buchmeiser其他文献
Professor Dr. Michael R. Buchmeiser的其他文献
{{
item.title }}
{{ item.translation_title }}
- DOI:
{{ item.doi }} - 发表时间:
{{ item.publish_year }} - 期刊:
- 影响因子:{{ item.factor }}
- 作者:
{{ item.authors }} - 通讯作者:
{{ item.author }}
{{ truncateString('Professor Dr. Michael R. Buchmeiser', 18)}}的其他基金
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 - 财政年份:2015
- 资助金额:
-- - 项目类别:
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 - 财政年份:2015
- 资助金额:
-- - 项目类别:
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 - 财政年份:2012
- 资助金额:
-- - 项目类别:
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 - 财政年份:2010
- 资助金额:
-- - 项目类别:
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 - 财政年份:2007
- 资助金额:
-- - 项目类别:
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 - 财政年份:2006
- 资助金额:
-- - 项目类别:
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 - 财政年份:2006
- 资助金额:
-- - 项目类别:
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 - 财政年份:
- 资助金额:
-- - 项目类别:
Research Grants
相似国自然基金
Simulation and certification of the ground state of many-body systems on quantum simulators
- 批准号:
- 批准年份:2020
- 资助金额:40 万元
- 项目类别:
Cortical control of internal state in the insular cortex-claustrum region
- 批准号:
- 批准年份:2020
- 资助金额:25 万元
- 项目类别:
微波有源Scattering dark state粒子的理论及应用研究
- 批准号:61701437
- 批准年份:2017
- 资助金额:28.0 万元
- 项目类别:青年科学基金项目
相似海外基金
EA: Upgrading the Geophysics Computing Facility at Arizona State University
EA:升级亚利桑那州立大学的地球物理计算设施
- 批准号:
2348594 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Standard Grant
REU Site: Sustainable Physics at Penn State: From the Subatomic to the Cosmos
REU 网站:宾夕法尼亚州立大学的可持续物理学:从亚原子到宇宙
- 批准号:
2349159 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Continuing Grant
STTR Phase I: Advanced Lithium Metal Anodes for Solid-State Batteries
STTR 第一阶段:用于固态电池的先进锂金属阳极
- 批准号:
2335454 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Standard Grant
Robust Transient State Estimation for Three-Phase Power Systems
三相电力系统的鲁棒瞬态估计
- 批准号:
2330377 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Standard Grant
SBIR Phase II: Sodium-Based Solid-State Batteries for Stationary Energy Storage
SBIR第二阶段:用于固定储能的钠基固态电池
- 批准号:
2331724 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Cooperative Agreement
CAREER: Harnessing Dynamic Dipoles for Solid-State Ion Transport
职业:利用动态偶极子进行固态离子传输
- 批准号:
2339634 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Continuing Grant
Fire-retardant Solid State Electrolytes for Rechargeable Li-ion Batteries
用于可充电锂离子电池的阻燃固态电解质
- 批准号:
DP240102728 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Discovery Projects
Understanding the mechanosynthesis mechanism of solid-state electrolytes via in-situ synchrotron XRD
通过原位同步加速器 XRD 了解固态电解质的机械合成机制
- 批准号:
24K17553 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Grant-in-Aid for Early-Career Scientists
Probing the origin and evolution of low-oxidation state iron and copper nanoparticles in the brain
探究大脑中低氧化态铁和铜纳米粒子的起源和演化
- 批准号:
EP/X031403/1 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Research Grant
Near-room Temperature Solid-state Hydrogen Storage
近室温固态储氢
- 批准号:
EP/Y007778/1 - 财政年份:2024
- 资助金额:
-- - 项目类别:
Research Grant