Redox active ligands allow for new avenues of reactivity that go beyond traditional inorganic or organometallic reactivity. These ligands play a role beyond being a spectator, whether it is allowing for enhanced metal-ligand cooperativity, multiple proton and electron transfer, or stabilization of unusual metal oxidation states. The incorporation, design, and reactivity of redox active ligand metal complexes provide a rich, new area of chemistry to explore.The chemistry of a bis(catechol) ligand, XbicH4, formed from Schiff base condensation of 1,8-diamino-9,9-dimethylxanthene with 4,6-di-tert-butylcatechol-3-carboxaldehyde was explored with silicon and zirconium. When metalated by silicon to form [(XbicH2)SiPh]+, the complex adopts a five-coordinate, square pyramidal geometry, where silicon lies above the plane of the two catechols with an apical phenyl ring. Zirconium complexes are formed by reaction of XbicH4 with (TPP)Zr(OAc)2, to yield heteroleptic (TPP)Zr(XbicH2), or with Zr(acac)4, to give the homoleptic Zr(XbicH2)2. In both the silicon and zirconium complexes, XbicH2 binds to the metals in the catecholate-iminium form. The imines of these complexes can be deprotonated, to give a complexes of the fully deprotonated Xbic[4-] ligand. Deprotonation with alkali metal bases results in heterobimetallic complexes with the alkali metal cation adopting a pentagonal monopyramidal geometry in the lower bis(imine) pocket. Some of the eight-coordinate bis(catecholate) zirconium complexes show fluxional behavior, an uncommon occurrence in analogous eight-coordinate bis(porphyrin) zirconium complexes. Elucidation of the mechanism has been carried out through VT-NMR and by DFT calculations, which suggest that a seven-coordinate intermediate plays a significant role in the dynamic behavior.Different oxidation states of the bis(catecholate) silicon complexes were found to be inaccessible. The bis(catecholate) zirconium complexes show rich cyclic voltammograms and optical spectra that revealed that oxidation of these compounds is possible, with (TPP)Zr(XbicH2) showing two ligand-centered redox waves and Zr(XbicH2)2 showing four redox waves. The analogous deprotonated zirconium compounds show similar redox waves, but at lower potentials. Complete oxidation of Na2[(TPP)Zr(Xbic)] with two equivalents of FcPF6 gives the fully oxidized (TPP)Zr(Xbis)•NaPF6, with a sodium ion bound in the lower pocket (Xbis = 9,9-dimethylxanthene-bis(imine)-bis(semiquinone)). This is the first known bis(semiquinonate) zirconium complex that has been fully characterized spectroscopically and structurally. The oxidized zirconium complex dehydrogenates hydrazobenzene, forming azobenzene and (TPP)Zr(XbicH2).Complexes of the late transition metal iridium with redox-active iminoxolene ligands can be accessed by reactions of iridium(I) precursors with the bulky iminoquinone N-(2,6-diisopropylphenyl)-3,5-di-tert-butyl-o-iminobenzoquinone (Diso). This five-coordinate complex, (Diso)2IrCl, adopts a distorted square pyramidal structure with an apical chloride ligand. This complex undergoes halide exchange to form an air-stable iridium iodide complex, (Diso)2IrI. (Diso)2IrCl binds to neutral donors, such as pyridine, and isomerizes from a trans to cis geometry. 1H NMR spectra of the cis-pyridine iridium complexes reveal the existence of a low-lying triplet state. Oxidation of (Diso)2IrCl by one electron leads to formation of air-stable trans and cis-(Diso)2IrCl2 complexes. Conversely, (Diso)2IrCl can be reduced by one electron to form (Diso)2Ir. Structural and spectroscopic features of these complexes indicate a degree of covalency between the metal and the ligands, with the amount of π donation from ligand to metal dependent on the oxidation state of the metal.The reaction of (Diso)2IrCl with oxygen atom transfer reagents produces discrete iridium alkoxide complexes derived from oxidation of the isopropyl groups of the Diso ligand as products. These oxidized alkoxide iridium products suggest the formation of a reactive iridium-oxo intermediate, which goes on to perform C-H activation. Mechanistic studies show the existence of an intermediate that can be intercepted with base and affects the product distribution of the two iridium alkoxide complexes. Kinetic isotope competition studies, via an intramolecular competition between reaction with the C-H vs. C-D bond of the isopropyl methine carbon, are done using different oxygen atom transfer reagents. KIE ratios of 10 are obtained, regardless of the nature of the oxidant, and suggests that transfer of a hydrogen atom is part of the product-determining step. These KIE results show that the oxidation reactions proceed through a common intermediate and that the intermediate is not a complex with the oxidant. While reaction of (Diso)2IrCl and OAT donors yield iridium alkoxides, reacting (Diso)2IrCl with molecular oxygen yields entirely different products. Spectroscopic data suggests that initially, there is formation of an O2-bound iridium complex, with the dioxygen bridged across the iridium metal and a carbon of one of the iminoxolene C=O bond. Rather than forming alkoxide complexes, this reaction undergoes ring cleavage of one of the iminoxolene ligands. This is highly suggestive of peroxo chemistry when (Diso)2IrCl reacts with molecular oxygen, rather than metal-oxo chemistry. Reaction of (Diso)2Ir, a lower oxidation state of (Diso)2IrCl, produces an iridium-alkyl bond with one of the isopropyl groups on the Diso ligand. Different iminoxolene ligands were synthesized and complexed with iridium, but produces a distribution of four-, five-, or six-coordinate complexes, unlike Diso, which only produces the five-coordinate complex.