The synthesis of four rhodium(II) paddlewheel complexes bearing axial aromatic amines and coumarin ligands, with formula [Rh 2 (OAc) 4 (L) 2 ] (L = NH 2 Mesityl (1), NH 2 Dip (2), NH 2 Couma (3), coumarin (4)), prompted by microwave irradiation, was carried out successfully. All of the complexes were characterized by the melting point, elemental analysis, NMR, IR, and UV/Visible spectroscopy. Additionally, the structure of complexes 1-2 and 4 was corroborated by single-crystal X-ray diffraction. Cyclic voltammetry, ESI-MS, and tandem MS analyses were carried out in compound 1 for gaining further insight into its stability. Finally, a DFT study shows that complexes 1-4 are the thermodynamic products, having as intermediates complexes 1 -4 which, under our experimental conditions, cannot be isolated.