Investigating Hydroamination with Ammonia by Main Group Complexes

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.

The primary impact of the OxICFM CDT will be the highly-trained world-class scientists that it delivers. This impact will encompass both the short term (during their doctoral studies), the medium term (subsequent employment) and ultimately the longer timescale defined by their future careers and consequent impact on science, engineering and policy in the UK.

The impact of OxICFM students during their doctoral studies will be measured by the culture change in graduate training that the Centre brings about - in working at the interface between inorganic synthesis and manufacturing, and fostering cross-sector industry/academia working practices. By embedding not only from larger companies, but also SMEs, we have developed a training regime that has broader relevance across the sector, and the potential for building bridges by fostering new collaborations spanning enormous diversity in scientific focus and scale. Moreover, at a broader level, OxICFM offers to play a unique role as a major focus (and advocate) for manufacturing engagement with academic inorganic synthetic science in the UK.

From a scientific perspective, OxICFM will be uniquely able to offer a broad training programme incorporating innovative and challenging collaborative projects spanning all aspects of fundamental and applied inorganic synthesis, both molecular and materials based (40+ faculty). These will address key challenges in areas such as energy provision/storage, catalysis, and resource provision/renewal necessary to enhance the capability and durability of UK plc in the medium term. To give some idea of perspective, the output from previous CDTs in Oxford's MPLS Division include two start-up companies and in excess of 30 patents.

It is not only in the industrial and scientific realms that students will have impact during their timeframe of their doctorate. Part of the training programme will be in public engagement: team-based challenges in resource development/training and outreach exercises/implementation will form part of the annual summer school. These in turn will constitute a key part of the impact derived from the CDT by its engagement with the public - both face-to-face and through electronic/web-based media. As the centre matures, our aspiration is that our students - from diverse backgrounds - will act as ambassadors for the programme and promote even higher levels of inclusion from all parts of society.

For our partners, and businesses both large and small in the manufacturing sector, it will be our students who are considered the ultimate output of the OxICFM CDT. Our programme has been shaped by the need of such companies (frequently expressed in preliminary discussions) to recruit doctoral graduates who can apply themselves to a broad spectrum of multi-disciplinary challenges in manufacturing-related synthesis. OxICFM's cohort-based training programme integrates significant industry-led training components and has been designed to deliver a much broader skill set than standard PhD schemes. The current lack of CDT training at the interface of inorganic chemistry and manufacturing (and the relevance of inorganic molecules/materials to numerous industrial sectors) heightens the need for - and the potential impact of - the OxICFM CDT. Our students will represent a tangible and valuable asset to meet the long-term skills demand for scientists to develop new materials and nanotechnology identified in the UK Government's 2013 Foresight report.

In the longer term, the broad and relevant training delivered by OxICFM, and the uniquely wide perspective of the manufacturing sector it will deliver, will allow our graduates to obtain (and thrive in) positions of significant responsibility in industry and in research facilities/institutes. Ultimately we believe that many will go on to be future research leaders, driving innovation and changing research culture, and thereby making a lasting contribution to the UK economy.