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Bespoke Bimetallics for Chemical Cooperativity

用于化学协同性的定制双金属

基本信息

批准号：
EP/S029788/1
负责人：
Robert Mulvey
金额：
$ 72.52万
依托单位：
University of Strathclyde
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2019
资助国家：
英国
起止时间：
2019 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FS029788%2F1
关键词：
Bespoke Bimetallics Chemical Cooperativity

项目摘要

The importance of the UK's chemical and pharmaceutical sector can be seen in the statistic that it supplies £60M of added value each working day (that equates to £15bn a year) to our Gross Domestic Product (the total value of goods and services provided by a country in one year). Cutting edge research, innovation and sustainability lie at the heart of this project. The research is in organometallic chemistry, a core area of chemistry that is utilised in a myriad of real world applications, spanning chemistry and other disciplines such as biochemistry and material science. Organometallic compounds, comprising an organic moiety and a metal moiety are essential tools for constructing molecules big and small. A large proportion of known chemical processes depend on the metal moiety of organometallic compounds being a precious transition metal (commonly palladium, platinum, rhodium, iridium, ruthenium, and osmium), which are essential for the manufacture of numerous specialty chemicals from agrochemicals through to pharmaceuticals (especially anticancer drugs).Base (non-precious) metals are generally much cheaper (due to their higher natural abundance) and reflecting this high abundance in the earth's crust they have less toxicity concerns than their precious metal counterparts. The problem is their chemistry (their ability to carry out useful reactions efficiently) is rather limited by comparison so more often than not they are inefficient in many chemical processes. If base metal chemistry could be developed to the status of precious transition metal chemistry or better still to go beyond this status, then sustainability would be significantly improved and reliance on less environmentally benign precious transition metals would be reduced.Recent advances by the research team have demonstrated that base chemistry can be made orders of magnitude more efficient by preparing organometallic compounds that contain two base metal elements instead of one. The metal common to all of these metal pairs is an alkali metal (lithium, sodium or potassium), while the second metal is magnesium, zinc, aluminium or the earth-abundant transition metals iron and manganese. By forming mixed-metal bimetallic structures impossible in single-metal systems, cooperative effects are induced which transform the reactivity of the base metals opening up a vast number of novel reactions that are currently inaccessible to base metals on their own. Cooperativity will be especially important in our targeted C-C bond formations and C-F bond activations through alkali metal -Fe or -Mn partnerships as currently these reactions are generally the domain of precious transition metal catalysis. Realising this escalation of sustainable base metal chemistry will be a major breakthrough in itself but this project will take on an additional ambitious challenge. Alkali metal organometallic chemistry invariably needs to be performed under anaerobic conditions as the compounds involved rapidly decompose with even traces of air or moisture. However, the team recently made the extraordinary finding that certain organoalkali metal reactions could be run under aerobic conditions by using Deep Eutectic Solvents (DES) as opposed to industry standard classical organic solvents. DES are more cost-effective, greener and biorenewable than organic solvents and switching to them would also do away with the need for costly inert atmosphere protocols. The proof of concept results with DES have been with single base metals, so the challenge is to develop this new bimetallic chemistry in DES. Success will impact the practice of organometallic chemistry worldwide.

英国化学和制药行业的重要性可以从统计数据中看出，它每个工作日为我们的国内生产总值（一个国家在一年内提供的商品和服务的总价值）提供6000万英镑的附加值（相当于每年150亿英镑）。尖端的研究、创新和可持续性是这个项目的核心。该研究是在有机金属化学，化学的一个核心领域，在无数的现实世界的应用，跨越化学和其他学科，如生物化学和材料科学。由有机部分和金属部分组成的有机金属化合物是构建大大小小的分子的基本工具。已知化学过程的很大一部分依赖于有机金属化合物的金属部分，这些金属部分是一种珍贵的过渡金属（通常是钯、铂、铑、铱、钌和锇），它们对于从农用化学品到药品（特别是抗癌药物）的许多特殊化学品的制造是必不可少的。碱金属（非贵金属）通常要便宜得多（由于它们的天然丰度较高），并且反映了地壳中这种高丰度，它们的毒性问题比贵金属同行要小得多。问题是它们的化学性质（它们有效地进行有用反应的能力）相比之下相当有限，因此它们在许多化学过程中往往效率低下。如果贱金属化学能够发展到贵重过渡金属化学的地位，或者更好地超越这种地位，那么可持续性将大大提高，对不太环保的贵重过渡金属的依赖将减少。研究小组的最新进展表明，通过制备含有两种而不是一种贱金属元素的有机金属化合物，可以使基础化学的效率提高几个数量级。所有这些金属对共有的金属是碱金属（锂、钠或钾），而第二种金属是镁、锌、铝或地球上丰富的过渡金属铁和锰。通过形成单金属体系中不可能形成的混合金属双金属结构，诱导了协同效应，从而改变了贱金属的反应性，开辟了大量目前贱金属本身无法实现的新反应。在我们的目标C-C键形成和通过碱金属-Fe或-Mn伙伴关系激活C-F键时，协同性将特别重要，因为目前这些反应通常是贵重过渡金属催化的领域。实现可持续贱金属化学的升级本身将是一个重大突破，但该项目将承担额外的雄心勃勃的挑战。碱金属有机金属化学总是需要在厌氧条件下进行，因为所涉及的化合物即使有微量的空气或水分也会迅速分解。然而，该团队最近取得了非凡的发现，通过使用深度共晶溶剂（DES）而不是工业标准的经典有机溶剂，某些有机碱金属反应可以在有氧条件下进行。与有机溶剂相比，DES更具成本效益、更环保、更可再生，改用它们也将不再需要昂贵的惰性气氛协议。使用DES的概念验证结果是针对单一贱金属的，因此挑战是在DES中开发这种新的双金属化学。成功将影响全球有机金属化学的实践。

项目成果

期刊论文数量（10）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Alkali Metal Dihydropyridines in Transfer Hydrogenation Catalysis of Imines: Amide Basicity versus Hydride Surrogacy

碱金属二氢吡啶在亚胺转移氢化催化中的作用：酰胺碱度与氢化物替代

DOI：
10.1002/ange.202304966
发表时间：
2023
期刊：
Angewandte Chemie
影响因子：
0
作者：
Macdonald P
通讯作者：
Macdonald P

Heavy Alkali Metal Manganate Complexes: Synthesis, Structures and Solvent-Induced Dissociation Effects.

DOI：
10.1002/chem.202201716
发表时间：
2022-10-04
期刊：
CHEMISTRY-A EUROPEAN JOURNAL
影响因子：
4.3
作者：
Ballmann, Gerd M.;Gentner, Thomas X.;Kennedy, Alan R.;Hevia, Eva;Mulvey, Robert E.
通讯作者：
Mulvey, Robert E.

Alkali-Metal Mediation: Diversity of Applications in Main-Group Organometallic Chemistry.