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Iron-catalysed reactions have seen extensive focus and development in recent years, due in part to increasing focus on sustainable methodologies. However, a significant challenge to this continued development is a lack of fundamental understanding of the active species and reaction pathways that govern reactivity in iron-catalysed systems. This chapter highlights the challenges in studying open shell iron catalysis as well as techniques that can be effectively used to achieve the desired molecular level insight. While these have provided substantial insight into what has long been regarded as a “black box”, both the strengths and limitations of these techniques are presented alongside highlights of potential pitfalls using recent literature examples.

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