The thermolytic decomposition of Mo(CO)6 with hydrogen sulfide or ammonia vapor (in a He carrier stream) at temperatures ranging from 300 to 1100 °C produces high surface area molybdenum sulfides (MoS2 or Mo2S3) or molybdenum carbides (hexagonal Mo2C) and carbonitrides, (hexagonal MoN(C) or cubic Mo2N(C)), respectively. The MoS2 surface areas range from 16.7 to 82.0 m2/g, while the surface areas of molybdenum carbides and carbonitrides vary from 14.9 to 21.1 m2/g. The maximum surface area for MoS2 is achieved at 500 °C and decreases with increasing or decreasing temperature. The surface area of the carbonitrides formed from 300 to 800 °C increases with increasing temperature up to 950 °C, where lower surface area Mo2C is formed. Crystallographically pure hexagonal MoN is prepared by decomposing Mo(CO) 6 in pure ammonia. Fe(CO) 5 decompositions in ammonia produce FexZ (where 5.8≥x≥1.6 and Z=C and N), and in some cases elemental Fe. Hexagonal Fe3 N(C) forms when Fe(CO) 5 is thermolyzed in ammonia from 300 to 600 °C, with surface areas ranging from 9.5 to 13.7 m2/g, whereas orthorhombic Fe3C and cubic Fe are produced at 700, 800, 900 and 1000 °C with surface areas of 6.7, 7.6, 2.2 and 2.0 m2/g, respectively. Within the same phase, the surface areas of the carbonitrides increase with increasing reaction temperature. These iron and molybdenum carbonitrides catalyze the conversion of CO/H2 to alkanes and methanol. Based on preliminary catalytic studies, the highest rate of methane (2850 g/kg/hr at 374 °C) and methanol (440 g/kg/hr at 284 °C) formation was accomplished with an FeMo carbonitride prepared by decomposing Mo(CO)6 and Fe(CO)5 in ammonia at 800 °C.