There has been some effort in recent years to design iridium complexes with higher ET or complexes that are more strongly photoreducing. Typically, the principal approach for designing Ir(C^N)3 PCs with high ET is to introduce electron-withdrawing fluorine or trifluoromethyl substituents on the cyclometalating aryl groups of ppy-type ligands, thus stabilizing the HOMO and increasing ET. Indeed, fac-Ir(dFppy)3 has a higher ET (2.75 eV in MeCN) than fac-Ir(ppy)3 (2.50 eV in MeCN) and for this reason is often employed in EnT catalysis with more challenging substrates. Additionally, fac-Ir(Fppy)3 is more photoreducing (E*ox of -1.90 V vs. SCE in MeCN) compared to fac-Ir(ppy)3 (E*ox of -1.75 V vs. SCE in MeCN), while in the ground state the two complexes have effectively the same reducing power (Ered = -2.20 and -2.18 V vs. SCE in MeCN for fac-Ir(ppy)3 and fac-Ir(Fppy)3, respectively). Heteroleptic complexes of the type Ir(C^N)2(L^L) permit the HOMO and LUMO to be sequestered on different ligand, with the LUMO typically localized on the ancillary L^L ligand. When L^L is a paccepting ligand such as 2,2'-bipyridine (bpy), the redox potentials are generally balanced by more moderate compared to those of fac-Ir(ppy)3 and as such cationic photocatalysts such as [Ir(ppy)2(bpy)]PF6 are employed frequently in reactions proceeding via a reductive quenching mechanism. When the L^L ligand is electron-rich, such as β-diketiminates (NacNac), then the resulting PCs such as those developed by Teets and co-workers are strongly photoreducing (E*ox = -2.2 to -2.4 V vs. SCE). These were used in a number of challenging transformations, such as the dehalogenation of unactivated alkyl and aryl bromides and iodides , and the reduction of carbonyl substrates. However, for most transformations these PCs require a specific sacrificial reductant, 1,3-dimethyl-2,3-dihydro-2-phenylbenzimidazole (BIH) and elevated reaction temperatures (45 o C). Recently, Wenger and co-workers developed an iridium(III) isocyanoborato complex with an exceptionally high triplet energy (ET = 2.99 eV) for use in a range of photocatalytic transformations. This PC is capable of sensitizing substrates with exceptionally high ET (3.00 eV). In terms of photoredox catalysis, this PC (E*ox = -1.59 V and Ered = -2.4 V vs SCE in MeCN) could engage in dehalogenation and detosylation reactions of moderately difficult substrates (Ered = -2.0 to -2.2 V vs. SCE), as well as promote a photochemical degradation of lignin. Although this PC proved particularly promising for PEnT catalysis, its inherent drawbacks lie in a comparatively challenging ligand synthesis as compared to those for C^N, N^N ligands, as well as the C^C ligands discussed in this report. Moreover, complete photodegradation of the complex was observed after 60 minutes of irradiation at 415 nm in deuterated acetonitrile (MeCN-d3).