of diheteroaryl or diarylmanganese reagents prepared by directedmanganationusingTMP2Mn·2MgCl2·4LiCl. The resulting diorganomanganese reagents can efficiently undergo an oxidative dimerization leading to the homocoupling products in good yields. Remarkably, a number of functional groups, as well as sensitive heterocycles are tolerated using this metalation–dimerization procedure.