Investigating Hydroamination with Ammonia by Main Group Complexes

我的哲学博士研究的主要目标是开发通过加氢胺化生产伯胺的催化剂。伯胺是一类化学物质，其用另一个原子或原子团取代氨（NH 3）中的氢原子（H）。它们有着广泛的用途，从制药业到纺织业。它们对社会的重要性意味着化学工业一直在寻找制造胺的新方法，以减少浪费和减少能源密集度。氢化胺化是一种产生最少废物的胺制造方法。氢化胺化的一个例子是氨加成到C-C双键上。一个H连接到一个C，而另一个C键合到NH 2基团。该反应只需要两种原料，因此在该过程中不需要涉及其他反应物。氨价格便宜且储量丰富，而且C-C双键材料通常来源于化石燃料，因此价格也实惠。然而，如果没有催化剂，这个过程非常缓慢，需要大量的能量。催化剂允许分子通过需要较少能量的替代途径进行反应。重要的是，它不会在反应中耗尽，因此可以继续催化许多其他反应。通过加氢胺化制备伯胺的催化剂的开发将导致显著更便宜的胺。然而，更重要的是，这一过程对我们的环境影响要小得多，因为所需的能源更少，化学品的浪费也更少。这些优点使我的项目在工业和社会上都具有相关性，同时也具有学术意义。在20世纪90年代，能够将C-C双键加氢胺化的催化剂的开发被描述为催化研究界面临的十大挑战之一。这是一个尚未得到充分解决的挑战，然而，随着伯胺在全球范围内成为越来越多使用的化学原料，对解决方案的需求一直在增加。这使我的项目坚定地在EPSRC的制造未来的研究主题，并提出了一个要求，但有趣的项目，我的研究重点将是主族催化剂，这已经收到了显着较少的研究历史上的催化应用比系统包含过渡金属。尽管被用作许多工业过程的催化剂，但过渡金属的典型化学性质对催化加氢胺化产生了问题。相比之下，该项目将研究的系统具有化学性质，这意味着它们似乎不会面临这些问题，使它们成为进一步研究的明显候选者。此外，虽然有大量的研究为主族催化剂奠定了基础，但据我所知，迄今为止还没有发现，这使得这成为一个新的令人兴奋的研究途径。

The main aim of my DPhil research will be the development of a catalyst for the manufacture of primary amines by hydroamination. A primary amine is a class of chemical which has substituted a hydrogen atom (H) from ammonia (NH3) with another atom or group of atoms. They have widespread uses, from the pharmaceutical industry to textile manufacture. Their importance to society means that the chemical industry is always looking for new methods of manufacturing amines which reduce waste and are less energy intensive. Hydroamination is the method of amine manufacture which produces the least amount of waste.An example of hydroamination is the addition of ammonia to a C-C double bond. One H attaches to one C, whilst the other C bonds to the NH2 group. Only two starting materials are required for this reaction, so no other reactants need be involved during the process. Ammonia is cheap and abundant, and the C-C double bond material is typically derived from fossil fuels, so is also affordable. However, without a catalyst the process is very slow and requires lots of energy. A catalyst allows molecules to react via an alternate pathway which requires less energy. Importantly, it is not used up in the reaction, so can go on to catalyze many other reactions. The development of a catalyst for making primary amines by hydroamination would result in significantly cheaper amines. More importantly however, the process would have a much smaller impact on our environment - due to both less energy being required and reduced wastage of chemicals. These advantages make my project both industrially and societally relevant, as well as being academically interesting.In the 1990s the development of a catalyst capable of the hydroamination of C-C double bonds was described as one of the 10 largest challenges facing the catalytic research community. It is a challenge which has not yet been adequately solved, however the need for a solution has been increasing as primary amines become an increasingly used chemical feedstock globally. This places my project firmly within the EPSRC's Manufacturing the Future research theme and presents me with a demanding yet intriguing project.The focus of the research will be on main group catalysts, which have received significantly less research historically for catalytic applications than systems containing transition metals. Despite being deployed as catalysts for many industrial processes, the typical chemistry of transition metals creates problems for catalytic hydroamination. In contrast, the systems this project will investigate have chemical properties which mean they do not appear to face these issues, making them obvious candidates for further study. Furthermore, whilst there has been plenty of research laying the groundwork for a main group catalyst, to the best of my knowledge, none has been discovered as of yet, making this a new and exciting avenue of research.