The iron complex [(tBupyrr2pyr)Fe(OEt2)] ((tBupyrr2pyr) = 3,5-tBu2-bis(pyrrolyl)pyridine) adopts a unique cis-divacant octahedral geometry in which the OEt2 ligand is coordinated out of the plane of the tridentate ligand in an axial position, which is conserved under oxidizing and reducing conditions. Here we show that the cis-divacant octahedral geometry of iron complexes supported by the tBupyrr2pyr ligand can be harnessed to deazotate benzyl azide to benzaldimine ligands, leading to self-coupling of the benzaldimine ligands in two different ways. By using aryl azides with ortho-dimethyl substitution, the Csp3–H bonds of hydrocarbons can be aminated using [(tBupyrr2pyr)Fe(OEt2)] as a precatalyst. The S = 1 FeIV imido complex [(tBupyrr2pyr)Fe=N(2,6-Me2-4-tBu-C6H2)] capable of catalytic C–H bond amination was isolated and fully characterized by 57Fe Mössbauer spectroscopy, SQUID magnetometry, and computational studies. Further mechanistic studies establish a radical rebound mechanism with a remarkably high room temperature kinetic isotope effect value of 61.4(14.9). Exploration of other metal-ligand multiple bonds leads to isolation of a FeIII carbene radical complex [tBupyrr2pyrFeCPh2], which was studied by 57Fe Mössbauer and X-Ray absorption spectroscopies. Under thermolytic conditions, it was found that [tBupyrr2pyrFe(CPh2)] decomposes by carbene insertion into the 2-position of the pyrrolyl arm of the pincer ligand, followed by ring opening and dimerization to produce [{tBupyrr2py C(=CPh2)C(CMe3)=CHC(CMe3)=N}Fe]2 in a first order reaction with a negative entropy of activation of -87.6± 25.8 J·mol-1·K-1. Treatment of the dinuclear starting material [K2][(tBupyrr2pyrFe)2(m-N2)] with chalcogenide transfer reagents leads to isolation of the series of complexes [K2] [(tBupyrr2pyrFe)2(m-E)] (where E = O, S, Se, and Te), which show a decrease in the <Fe–E–Fe angle as E is varied down Group 16. This leads to an increase in the effective magnetic moment of the dinuclear complexes due to a decrease in antiferromagnetic coupling between the iron atoms. When [K2][(tBupyrr2pyrFe)2(m-N2)] is reduced with excess KC8 and two equivalents of 18-crown-6 (18-C-6) the mononuclear formally Fe0 complex [{K(18-C-6)}2(tBupyrr2pyr)Fe(N2)] is isolated. [{K(18-C-6)}2(tBupyrr2pyr)Fe(N2)] activates the C–H bond of benzene yielding [{K(18-C-6)}(tBupyrr2pyr)Fe(C6H5)], which can transfer the aryl group to ClBCat (Cat = catechol) yielding [{K(18-C-6)}(tBupyrr2pyr)Fe-Cl] and PhBCat. Finally, [{K(18-C-6)}(tBupyrr2pyr)Fe-Cl] can be reduced back to [{K(18-C-6)}2(tBupyrr2pyr)Fe(N2)] closing a synthetic cycle.