Significantly, neither Fe-catalyzed decarboxylative coupling (conditions A or B) necessitated O2 to turn over the catalytic cycle (Fe 2+ to Fe 3+ ), whereas recent work from our group(s) required an air atmosphere in conjunction with an Fe β-diketonate MHAT catalyst or cocatalyst. In the current work, the single iron(II) porphyrin turns over to iron(III) in the absence of oxygen by reaction with the RAE or its resultant radical: 1 H NMR studies demonstrated that Fe(TPP) will complex n-pentyl-CO(NHPI) prior to formation of n-pentyl-Fe(TPP) (see SI). Fe(TPP) can be formed from its corresponding hydride by either hydrogen evolution or alkene MHAT (see SI). As a result, Fe(TPP)Cl mimics the polyfunctionality of precious metals in innersphere (coordinative) alkene functionalization catalysis, but does so in a unique outer-sphere (noncoordinative) series of elementary steps. In the case of RAE-RAE coupling, the use of Zn metal is well-precedented to reductively decompose NHPI esters into carbon centered radicals.