The dearomatization of naphthalene and anthracene is explored by their η 2 coordination to {TpMo-(NO)(MeIm)} and {TpMo(NO)(DMAP)} (where Tp = hydridotris(pyrazolyl)borate, MeIm = 1-methylimidazole, and DMAP = 4-(dimethylamino)pyridine). The DMAP and MeIm complexes have nearly identical redox properties and abilities to bind these polycyclic aromatic hydrocarbons (PAHs), but unlike MeIm, the DMAP ligand can be protonated at N while remaining bound to the metal. This action enhances the πacidic properties of DMAP, resulting in greater stability of the molybdenum toward oxidation by acid. Utilizing this feature of the DMAP ligand, several new 1,2-dihydronaphthalenes and 1,2-dihydroanthracenes were prepared. Furthermore, it was found that acetals and Michael acceptors could function as electrophiles for the PAHs using the DMAP system, resulting in several new mono-and 1,4-dialkylated products.