The use of copper and iron complexes as cross-coupling catalysts is now a challenge in today organic synthesis, due to their low cost and low toxicity. This work, in a first part, deals with mechanistic insights into C-N and C-O cross-couplings catalyzed by copper complexes. In a second part, the true role of iron in C-N cross-couplings processes is investigated. In a third part, two examples of iron-catalyzed C-C bond formations are investigated: a Kochi-type coupling between an aryl halide and a Grignard reagent, and a radical carbocyclization. Cyclic voltammetry, theoretical DFT calculations, NMR and EPR spectroscopies have been used as investigation tools.