C-H Activation with Earth-Abundant Metals

C–H functionalisation offers the most sustainable method for chemical synthesis. The ability to selectively couple two fragments using nothing more than ubiquitous C–H bonds remains a grand challenge in chemistry and key enabler of wider science. Transition-metal-catalysed systems for C–H functionalisation based on precious metals (e.g. Pd, Pt, Rh and Ir) have dominated methods development in this area for the past 50 years, leading to systems which permit the direct functionalisation of C-H bonds to introduce a variety of new functionalities including C–C, C–O, C–N and C–B bonds. However, the increasing drive for sustainable catalytic methods has motivated the development of Earth-abundant metal catalysts for C–H functionalisation.

Our group is focused on mechanistic studies of current state-of-the-art systems for iron-catalysed C-H activation as well as the development of new classes of Earth-abundant metal catalysts for these reactions.  To date, our work in this area has included the first experiment identification and structurally characterisation of the key cyclometalated low-spin iron(II) intermediates active in directed iron-catalysed C–H arylation and allylation with iron-bisphosphines and triazole directing groups and C-H methylation with AlMe3. 

Selected Publications

• Boddie, T. E.; Carpenter, S. H.; Baker, T. M.; DeMuth, J. C.; Cera, G.; Brennessel, W. W.; Ackermann, L.; Neidig, M. L. J. Am. Chem. Soc. 2019, 141, 12338-12345. 
   
• DeMuth, J. C.; Song, Z.; Carpenter, S. H.; Boddie, T. E.; Radovic, A.; Baker, T. M.; Gutierrez, O.; Neidig, M. L. Chem. Sci. 2021, 12, 9398-9407.
   
• Bhatia, S.; DeMuth, J. C.; Neidig, M. L. Chem. Commun. 2021, 57, 12784-12787.