AbstractThe decomposition and reduction of ferrocene, an important precursor for iron chemical vapor deposition and catalyst for nanotube synthesis, is investigated in the gasâphase. Reactive intermediates are detected to understand the underlying chemistry by using a microreactor coupled to a synchrotron light source. Utilizing soft photoionization coupled with photoelectronâphotoion coincidence detection enables us to characterize exclusive intermediates isomerâselectively. A reaction mechanism for the ferrocene decomposition is proposed, which proceeds as a twoâstep process. Initially, the molecule decomposes in a homogeneous surface reaction at temperatures <900 K, leading to products such as cyclopentadiene and cyclopentadienyl radicals that are immediately released to the gasâphase. At higher temperatures, ferrocene rapidly decomposes in the gasâphase, losing two cyclopentadienyl radicals in conjunction with iron. The addition of hydrogen to the reaction mixture reduces the decomposition temperature, and changes the branching ratio of the products. This change is mainly attributed to the Hâaddition of cyclopentadienyl radicals on the surface, which leads to a release of cyclopentadiene into the gasâphase. On the surface, ligand fragments may also undergo a series of catalytic Hâlosses leading most probably to a high carbon content in the film. Finally, Arrhenius parameters for both global reactions are presented.