Reactions of laser-ablated osmium and iron atoms with CO and N(2) mixtures in excess neon have been investigated using matrix isolation infrared spectroscopy. The (NN)(x)MCO (M = Os, Fe; x = 1, 2) complexes are formed as reaction products during sample deposition and on annealing. These reaction products are characterized on the basis of the results of isotopic substitution, mixed isotopic splitting patterns, stepwise annealing, broad-band irradiation, and change of reagent concentration and laser energy. Density functional theory calculations have been performed on these products. Overall agreement between the experimental and calculated results supports the identification of these species from the matrix infrared spectra. The bonding characteristics and reaction mechanisms have been discussed. The M-C bonds are stronger than the M-N bonds in the same molecules. The formation of metal carbonyl dinitrogen complexes from the addition of CO to metal dinitrogen complexes is found to be more energetically favorable than that from the reactions of N(2) with metal carbonyls.