Investigating Hydroamination with Ammonia by Main Group Complexes

Lead Research Organisation: University of Oxford
Department Name: OxICFM CDT

Abstract

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.

Publications

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Studentship Projects

Project Reference Relationship Related To Start End Student Name
EP/S023828/1 01/04/2019 30/09/2027
2329463 Studentship EP/S023828/1 01/10/2019 30/09/2023 Lewis Wales