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Title: Structure and enhanced reactivity of chromocene carbonyl confined inside cavities of NaY zeolite
Authors: Estephane, Jane 
Groppo, Elena
Damin, Alessandro
Vitillo, Jenny G.
Gianolio, Diego
Lamberti, Carlo
Bordiga, Silvia
Prestipino, Carmelo
Nikitenko, Sergej
Quadrelli, Alessandra Elsje
Taoufik, Mostafa
Basset, Jean Marie
Zecchina, Adriano
Affiliations: Department of Chemical Engineering 
Issue Date: 2009
Part of: Journal of physical chemistry C
Volume: 113
Issue: 17
Start page: 7305
End page: 7315
Chromocene (Cp2Cr) hosted inside the supercage cavities of a NaY zeolite undergoes a structural distortion induced by the strong local electric fields generated by charge balancing counterions. This effect, clearly observed by an in situ Cr K-edge extended X-ray absorption fine structure (EXAFS) study, is the key factor in enhancing the reactivity of Cp2Cr toward CO. The Cp2Cr(CO) adducts initially formed are not as stable as when hosted in nonpolar environments such as toluene solution or polystyrene. The presence of strong anionic/ cationic pairs (Y-/Na+) favors, in a CO atmosphere, the loss of a Cp ring driven by an electron transfer mechanism (accompanied by ligand rearrangement) that results in the formation of the charged [CpCr(CO)3]- and [Cp2Cr(CO)]+ carbonyl species that are stabilized by Na+ and Y- pairs. 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 disproportionation. Fast Fourier transform infrared (FTIR) spectroscopy, working in operando conditions, allows us to follow the time evolution of the IR stretching modes peculiar of reactants and products and thus to infer a reaction mechanism. The combination of quantum mechanical calculation with an in situ EXAFS study supports the hypothesis made on the basis of IR results. The work is further demonstration that 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 metallocene reactivity inside a polar matrix can be extremely useful to understanding their properties in polymerization conditions, where they are usually found as part of an ion pair, together with the anionic form of the activator (e.g., MAO).
Open URL: Link to full text
Type: Journal Article
Appears in Collections:Department of Chemical Engineering

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