Reactions of iron atoms with benzene

The reaction of iron atoms with benzene has been studied for nearly 40 years. Despite this, there is no agreement as to the nature of the products. With the aid of density functional theory calculations of the energetics and the infrared spectra of the various species, the present work provides a rationalization of the conflicting reports regarding the nature of the products of the reaction of iron atoms with benzene in low-temperature matrices. At low temperature in dilute benzene matrices, Fe(eta(6)-C(6)H(6)) and Fe(eta(6)-C(6)H(6))(2) are the major products. At high iron concentrations, Fe(2)(eta(2)-C(6)H(6)) is also formed. In pure benzene at low temperature, Fe(eta(6)-C(6)H(6))(2) and Fe(eta(6)-C(6)H(6))(eta(4)-C(6)H(6)) are formed. None of the species undergo photoexcitation to give insertion products HFe(C(6)H(5)). In pure benzene at 77 K, Fe(eta(6)-C(6)H(6))(eta(4)-C(6)H(6)) is the major product, together with small amounts of Fe(eta(6)-C(6)H(6))(2) and iron clusters. The infrared spectra of pure benzene are complicated by the activation of infrared forbidden modes by the presence of the metal atom.