The reaction of M(O2CMe)(2), 4H(2)O (M) Ni, Co) with NaN3 in pyridine/MeOH under microwave irradiation and controlled pressure/temperature leads to the formation of the trimetallic species [M-3-(N-3)(3)(O2CMe)(3)(py)(5)] (M) Ni, 1; Co, 2) in 4 min and in high yields. Both complexes display dominant ferromagnetic interactions and high-spin ground states.