The past three decades have witnessed major developments in Pd-catalyzed C-N cross-coupling of amines with aryl halides to form anilines, a common structure found in bioactive drug molecules. Many Pd-catalyzed methods rely on the use of sterically bulky ligands and elevated temperatures to facilitate reductive elimination from a destabilized metal center. We envisioned that a general and complementary method for C-N bond formation could be developed through the destabilization of a metal amido complex via either an electron or energy transfer process, thus providing an alternative approach to the use of structurally complex ligand systems and harsh conditions. Building off our previous efforts in C-S crosscoupling, we explored the engagement of aminyl radicals in Ni-catalyzed cross-coupling (Figure ). Gratifyingly, the arylation of anilines was achieved when pyridine was replaced with triethylamine. We proposed a mechanism that involves a Ni(I/II/III) catalytic pathway whereby a photoexcited *Ir(III) catalyst (E1/2 = +1.21 V vs SCE) oxidizes the aniline to form the anilinium radical cation, which upon deprotonation forms anilinium radical. Emission quenching studies show that aniline is a more effective quencher of the photocatalyst excited state than triethylamine. The trapping of the N-centered radical by a Ni(I) halide complex forms a Ni(II)amido complex. Reduction of the Ni(II) amido complex by Ir(II) gives a Ni(I)-amido complex that can undergo oxidative addition to the aryl halide to form a Ni(III)amido(Ar)(X) complex with the concomitant regeneration of the Ir(III) photocatalyst. Reductive elimination from the Ni(III) complex affords the desired product and Ni(I) complex. Distinct from C-S cross-coupling, Ni(0) catalysts are also competent catalysts in this reaction suggesting that an alternative mechanism such as energy transfer may also be operative (vide infra). In the preparative reactions, several electronically diverse anilines and sulfonamides could be chemoselectively cross- coupled with a variety of aryl iodides and bromides and the reactions possess high functional group tolerance. Limitations of this photochemical approach are the inferior performance of secondary anilines and alkylamines in the crosscoupling. MacMillan lab in collaboration with Buchwald lab concurrently reported metallaphotoredox arylation of alkylamines. Contemporaneously with our efforts, the Baran lab developed an electrochemical approach leveraging paired electrolysis outside the scope of our existing collaborative efforts (Figure ). 101-102 Intriguingly, the mechanistic underpinnings of the electrochemically driven C-N crosscoupling are distinct from the photochemical approach and access an orthogonal set of chemical space. While the photochemical approach previously described excels at coupling anilines and poorly tolerates alkyl amines, the electrochemical approach follows the opposite trend. A careful analysis of the two mechanisms reveals the origin of this observation. Critical to the success of this reaction is the oxidation of Ni(II) to Ni(III) to promote a challenging reductive elimination. Additionally, by relying on a base-mediated nitrogen atom activation over a radical oxidative approach, the reaction covers a range of nucleophilic alkyl amines with otherwise unstable radical species. However, poorly nucleophilic nitrogen coupling partners fail. Concerning the aryl coupling partner, a wide range of (hetero)aryl (pseudo)halides are tolerated. The Baran lab demonstrated several powerful applications of this reaction in preparing N-arylated oligonucleotides, polypeptides, and DNA-encoded libraries, which is a testament to the mild conditions of electrochemical redox control. Additionally, the reaction can be scaled to deliver decagram quantities of a product by employing a recirculating flow setup.