Multidentate ligands usually show great activities in low loading organometallic catalysis in palladium. Among these ligands, the use of ferrocenyl polyphosphane ligands give interesting results. Robust palladium-ferrocenyl triphosphane catalytic systems have permitted to obtain biarylamines and aryl-heteroaryl ethers in the presence of low catalytic loadings. DFT studies on catalytic cycle during formation of aryl-heteroaryl ethers were carried out. The presence of third phosphino group stabilizes a transition state which enhances the rate of the reductive elimination. Triarylamines were obtained with ferrocenyl diphosphane in the presence of 2 mol% of palladium loading. Moderate to excellent results were obtained. Finally, aryl-heteroaryl sulfides were obtained with excellent results with ferrocenyl tetraphosphane ligand in the presence of 0.2 mol% of palladium.