Details of Grant 

EPSRC Reference:	EP/Y019954/1
Title:	Synergistic Spectroscopy and Reactivity Studies to Revolutionise Iron-Catalysed C-H Functionalisation
Principal Investigator:	Neidig, Professor M
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	Oxford Chemistry
Organisation:	University of Oxford
Scheme:	Standard Research
Starts:	01 August 2024	Ends:	31 January 2028	Value (£):	530,742
EPSRC Research Topic Classifications:	Catalysis & Applied Catalysis Co-ordination Chemistry
EPSRC Industrial Sector Classifications:	No relevance to Underpinning Sectors
Related Grants:	EP/Y018664/1
Panel History:	Panel Date Panel Name Outcome 25 Oct 2023 EPSRC Physical Sciences Prioritisation Panel A October 2023 Announced
Summary on Grant Application Form
A long-standing goal of chemistry has been the ability to directly activate and functionalise C-H bonds. This would provide more efficient and direct routes to complex molecular architectures and circumvent the current multi-step methods often required to introduce specific functionalities. While transition metal catalysed systems for C-H functionalisation based on precious metals (e.g. Pd, Pt, Rh and Ir) have dominated methodological development in this area for the past 50 years, iron offers a truly sustainable future for catalysis due to the wide and high abundance, low environmental impact and minimal toxicity of iron salts. Yet iron-based methods remain uncompetitive and underdeveloped. For example, despite early studies by Fields and Tolman showing the potential of low oxidation-state iron species to undergo C-H metalation, attempts to render these reactions catalytic (in iron) have met with limited success. Alternative methods based on directed C-H functionalisation with iron and organometallic reagents have proven more successful, though the requirements for directing groups and the inherent functional group intolerance of organometallic reagents represent clear disadvantages that must be overcome to enable widespread adoption and synthetic use. Central to these challenges has been a reliance for iron-based methods to mimic palladium catalysis (ligands, reaction pathways, etc.) as opposed to developing bespoke ligands and mechanisms that utilise the unique reaction pathways available to iron. However, such ligand and catalyst design remains largely insurmountable due to a general lack of mechanistic understanding of iron C-H metalation, which still remains limited to the 50-year-old reports of Field and Tolman. This project will address this challenge using a new approach to catalyst development which directly pairs advanced inorganic spectroscopy/physical inorganic chemistry with reactivity studies to synergistically inform the development and understanding of novel catalytic methods. Detailed spectroscopy and reactivity studies our current iron-phosphine catalyst systems will be will enable the development the key structure-activity relationships that govern C-H metalation, mechanism and turnover. In turn, these insights and the established reactivity-understanding feedback loop (spectroscopy and reactivity) will be utilised to develop to overcome critical challenges in the field: (1) Alkane and alkene C-H functionalisation with iron; (2) Iron-catalysed C-H/nucleophile coupling without organometallic reagents. Further studies will leverage a new, general synthetic route to effective iron(0) complexes to develop new classes of iron(0) catalysts for C-H functionalisation in order to move beyond the reactivity limitations of existing iron phosphine systems. Overall, this work will enable the rational development of iron-based C-H functionalisation catalysts capable of breaking the current reliance of academia and industry on precious metal catalysis, and open new, sustainable, C-H functionalisation methods.
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Organisation Website:	http://www.ox.ac.uk