Structure and enhanced reactivity of chromocene carbonyl confined inside the cavities of NaY zeolite

Chromocene (Cp2Cr) hosted inside the supercage cavities of the NaY zeolite undergoes a structural distortion induced by the strong local electric fields generated by charge balancing counterions. This effect, clearly observed by in situ Cr K-edge EXAFS study, is the key factor in enhancing the reactivity of Cp2Cr towards CO. The Cp2Cr(CO) adducts initially formed are not as stable as when hosted in non-polar environments, such as toluene solution or polystyrene. The presence of strong anionic/cationic pairs (Y-/Na+) favors, in CO atmosphere, the loss of a Cp ring driven by an electron transfer mechanism (accompanied by ligand rearrangement) that results in the formation of charged [CpCr(CO)3] and [Cp2Cr(CO)]+ carbonyl species that are stabilized by the Na+ and Y- pairs. The shape selectivity of the supercage cavity of the Y zeolite is necessary for this reaction, as it can host the two Cp2Cr molecules needed for the disproportionation. Fast FTIR spectroscopy, working in operando conditions, allows to follow the time evolution of the IR stretching modes peculiar of reactants and products and thus to infer a reaction mechanism. Combination of quantum mechanical calculation with in situ EXAFS study supports the hypothesis made on the basis of IR results. The work demonstrates that the zeolitic voids act as “nanoscale reaction chambers”, where the reactivity of guest organometallic complexes can provide molecular insights into the elementary steps of heterogeneous catalysis. In this context, the investigation of metallocenes reactivity inside a polar matrix can be extremely useful to understand their properties in the polymerization conditions, where they are usually found as part of an ion-pair together with the anionic form of the activator (e.g. MAO).