Exploiting hemi-labile ligands in Main Group catalysis

在主族催化中利用半不稳定配体

• 批准号: 2714590
• 金额: --
• 依托单位: University of Oxford
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2022
• 资助国家: 英国
• 起止时间: 2022 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2714590
• 关键词: Exploiting; hemi; labile; ligands; Main

A catalyst is a substance which speeds up the rate of a chemical reaction without being consumed itself. They do this by offering an alternative, lower-energy mechanism by which the reaction happens, at the end of which the original catalyst is reformed. They are crucial for energy efficiency, as using them allows for reactions to be carried out quicker and at lower temperatures. As such, the use of catalysts is ubiquitous in industry for chemical processes of all types.The transition metals (the block of elements in the centre of the periodic table) make excellent catalysts, as their outermost electron shells are partially filled, allowing easy access to both electrons and empty binding sites around each metal atom. However, the metals which are important to catalysis, such as palladium and rhodium in catalytic converters for cars, tend to be toxic to life, expensive, and rare. As reserves in the Earth's crust dwindle, social and environmental difficulties have arisen with their supply and extracting them from their ores. It is vital, therefore, for replacements to be found.Elements belonging to the main group (on the right side of the periodic table, such as aluminium and silicon) tend to be much more benign environmentally and economically. Historically, these elements were thought to invariably form compounds with completed shells of electrons, making them poor catalysts. A series of more recent discoveries around this has challenged this view, and these elements are now known to undergo similar types of reaction to transition metals with a wide variety of molecules. Because of this, they are now currently being explored for use as catalysts.A ligand is a molecule which binds (or coordinates) to a central metal atom to form a coordination complex. A hemi-labile ligand is one which contains two or more sites which can coordinate, where at least one of them can reversibly dissociate, while the rest stay(s) firmlybound. This vacated space allows for other molecules to bind, which now allows a chemical reaction to easily occur.Hemi-labile ligands are now known to promote 'transition-metal' like behaviour in the main group elements where otherwise it would not be seen. A few promising potential catalysts have already been found by exploiting this behaviour. As such, this project aims expand upon this work and to develop efficient catalysts for a wider scope of important reactions.The ultimate objective is for the eventual replacement of transition metals with main group elements in catalysis. The potential impact is a more sustainable future, where chemical manufacturing is achieved solely using abundant, inexpensive, and environmentally benign elements.This project falls within the EPSRC 'Manufacturing the Future' research area.

催化剂是一种能加速化学反应而自身不被消耗的物质。他们通过提供一种替代的、低能量的反应机制来实现这一点，在反应结束时，原始催化剂被重新形成。它们对能源效率至关重要，因为使用它们可以在更低的温度下更快地进行反应。因此，催化剂的使用在所有类型的化学过程的工业中是无处不在的。过渡金属（元素周期表中心的元素块）是优秀的催化剂，因为它们的最外层电子层部分填充，允许容易接近每个金属原子周围的电子和空的结合位点。然而，对催化作用很重要的金属，如汽车催化转化器中的钯和铑，往往对生命有毒，昂贵且稀有。随着地壳储量的减少，在供应和从矿石中提取方面出现了社会和环境困难。因此，找到替代品至关重要。属于主族的元素（在元素周期表的右侧，如铝和硅）往往对环境和经济都要友好得多。从历史上看，这些元素被认为总是形成具有完整电子壳层的化合物，使它们成为不良催化剂。一系列最近的发现对这一观点提出了挑战，现在已知这些元素与过渡金属发生类似类型的反应，分子种类繁多。正因为如此，它们目前正被探索用作催化剂。配体是一种分子，它与中心金属原子结合（或配位）形成配位络合物。半不稳定配体是含有两个或更多个可以配位的位点的配体，其中至少一个位点可以可逆地解离，而其余的位点保持牢固结合。这种空出的空间允许其他分子结合，这使得化学反应更容易发生。半不稳定配体现在已知可以促进主族元素中的“过渡金属”样行为，否则它不会被看到。通过利用这种行为，已经发现了一些有前途的潜在催化剂。因此，本项目的目标是在此基础上进一步发展，为更广泛的重要反应开发高效催化剂，最终目标是在催化作用中用主族元素取代过渡金属。潜在的影响是一个更可持续的未来，在那里化学制造是完全使用丰富的，廉价的，和环境友好的元素实现。这个项目属于EPSRC的“制造未来”的研究领域福尔斯。