Transition-Metal Main-Group Cooperativity: A Strategy for Catalytic Transformations with Ammonia

University College London

Ammonia (NH3) is the most highly produced inorganic chemical, with more than 235 million tonnes manufactured globally in 2021. Direct functionalization of NH3 to produce amines would be a highly efficient method to generate value added chemicals used by the pharmaceutical, agrochemical, and polymer industries. Current methods to produce amines use stoichiometric or dangerous reagents, making these processes inherently wasteful and unsustainable. In this proposal, we aim to develop catalysts for the hydroamination of alkenes, alkynes, and the dehydrocoupling of arenes with NH3. Two of these transformations are currently not possible with any homogenous catalyst. Cooperative reactivity between elements has long been discussed as a potential solution to a range of challenging problems. This work aims to harness the known capacity of geometry constrained phosphines to activate NH3 and combine it with the ability of transition metals to react with hydrocarbon substrates. This will, for the first time, create cooperative catalysts which facilitate the hydroamination and dehydrocoupling of simple hydrocarbons with the commodity chemical ammonia.