Dual photoredox/nickel-catalysed C–N cross-couplings suffer from low yields for electron-rich aryl halides. The formation of catalytically inactive nickel-black is responsible for this limitation and causes severe reproducibility issues. Here, we demonstrate that catalyst deactivation can be avoided by using a carbon nitride photocatalyst. The broad absorption of the heterogeneous photocatalyst enables wavelength-dependent control of the rate of reductive elimination to prevent nickel-black formation during the coupling of cyclic, secondary amines and aryl halides. A second approach, which is applicable to a broader set of electron-rich aryl halides, is to run the reactions at high concentrations to increase the rate of oxidative addition. Less nucleophilic, primary amines can be coupled with electron-rich aryl halides by stabilizing low-valent nickel intermediates with a suitable additive. The developed protocols enable reproducible, selective C–N cross-couplings of electron-rich aryl bromides and can also be applied for electron-poor aryl chlorides.

双光氧化还原/镍催化的C–N交叉偶联的富电子芳基卤化物收率低。催化惰性镍黑的形成是造成这种局限性的原因，并导致严重的再现性问题。在这里，我们证明了通过使用氮化碳光催化剂可以避免催化剂失活。非均相光催化剂的广泛吸收使得能够以波长为基础控制还原消除的速率，以防止在环状仲胺和卤代芳基偶合期间形成镍黑。适用于更广泛的一组富电子芳基卤化物的第二种方法是在高浓度下进行反应，以提高氧化加成率。较少的亲核性 伯胺可以通过用合适的添加剂稳定低价镍中间体而与富电子芳基卤化物偶联。所开发的协议可实现富电子芳基溴化物的可重现，选择性C–N交叉偶联，也可用于贫电子的芳基氯化物。