The cluster complexes (μ-H)Os 3(μ-O CR)(СО) 10 (R = Me ( 1); R = Ph ( 2)) catalyze the allylic rearrangement of N-allylacetamide at room temperature. Microwave irradiation greatly (by more than several thousand-fold) accelerates the reaction between the solution of 2 and allylacetamide. The interaction of cluster 2 with allylamine both at room and elevated temperatures results in cleavage of the C–N bond and coordination of the allylic fragment to one of the osmium atoms with the formation of Os 3(CO) 9(μ,η 2-O C-Ph)(η 3-C 3H 5) ( 4) cluster.