The functionalization of C–H bonds remains a core area of interest in chemical catalysis and biological chemistry. Transition metals figure prominently in this area and operate via a range of mechanisms including oxidative addition to electron rich metals, metallation-deprotonation at electrophilic metals, and H-abstraction and rebound at high-talent metal oxos. We are exploring an alternate approach in which low-valent, high-spin Fe can weaken C–H bonds via pi-coordination, thereby enabling their cleavage by radical reagents that would otherwise have insufficient driving force to achieve C–H cleavage. This approach allows for the cleavage of sp, sp2, and sp3 C–H bonds at high-spin Fe. This reactivity, which can be viewed as a PCET approach to C–H bond cleavage and formation, may be relevant to bioorganometallic reactivity and models thereof.