Carbon monoxide hydrogenation using catalysts prepared via thermal decomposition of [(eta(5)-C5H5)Fe(CO)(2)M(CO)(5)], M = Mn, Re supported on gamma-alumina is described and discussed. The thermal decomposition of the complex is characterised using FTIR spectroscopy and thermal analysis and involves the formation of ferrocene in addition to small metal particles supported on gamma-alumina. CO hydrogenation studies indicate that the addition of Mn decreases the yield of C-1 products (methane and methanol) and increases catalyst activity. In contrast, addition of Re enhances the hydrogenation activity of the catalyst and decreases the probability of chain propagation. Carbon monoxide hydrogenation over a series of catalysts prepared via the thermal decomposition of [(eta(5)-C5H5)Fe(CO)(2)](2)-(mu-(CH2)(n)), n = 0, 3, 5 was also studied and the catalyst activity was observed to decrease with increasing n. The catalyst having n = 3 gave the lowest yield of C1 products for these iron containing catalysts.