The reaction pathways and kinetics of 4-(naphthylmethyl)bibenzyl (NBBM) were studied in an effort to resolve certain fundamentals underlying catalysis of coal liquefaction by Fe-based catalysts. Reaction of NBBM under a hydrogen atmosphere was performed for a series of iron carbonyl-based catalyst precursors : Fe(CO)(4)PPh(3), Fe(CO)(3)(PPh(3))(2), and Fe(CO)(2)(PPh(3))(2)CS2. The precursors’ activities for the disappearance of NBBM were Fe(CO)(4)PPh(3) > Fe(CO)(2)(PPh(3))(2)CS2 > Fe(CO)(3)(PPh(3))(2). All precursors gave significantly higher rates than that for thermal reaction at 400 degrees C. Thermolysis of NBBM was selective for cleavage at the bibenzyl bond, whereas the catalyst precursors were selective for cleavage at the naphthyl moiety. Hydrogenation activity was also observed for each of the three catalyst precursors. Possible catalytic reaction mechanisms are considered.