Organometallic complexes hosted inside porous frameworks are particularly interesting because of possible application in heterogeneous catalysis or electronic devices and optical materials. We present here a detailed spectroscopic investigation on the structure and reactivity towards simple reagents (such as CO) of chromocene molecules (Cp2Cr) encapsulated into the nanovoids of two different matrices: a non polar polystyrene (PS) and a polar NaY zeolite. We demonstrate that stable Cp2Cr(CO) complexes are formed in PS, while in NaY the presence of high internal electric fields confers to the Cp2Cr molecules a much higher reactivity towards CO. In situ EXAFS data, combined with other spectroscopic techniques and ab initio theoretical calculations, allowed the structural determination of the reaction products and afforded the full comprehension of the complex reactivity of Cp2Cr molecules inside the cavities of PS and NaY hosts.

Formation and reactivity of CrII carbonyls hosted in polar and non polar supports

GIANOLIO, DIEGO;GROPPO, Elena Clara;PRESTIPINO, Carmelo;ZECCHINA, Adriano;BORDIGA, Silvia;LAMBERTI, Carlo
2009

Abstract

Organometallic complexes hosted inside porous frameworks are particularly interesting because of possible application in heterogeneous catalysis or electronic devices and optical materials. We present here a detailed spectroscopic investigation on the structure and reactivity towards simple reagents (such as CO) of chromocene molecules (Cp2Cr) encapsulated into the nanovoids of two different matrices: a non polar polystyrene (PS) and a polar NaY zeolite. We demonstrate that stable Cp2Cr(CO) complexes are formed in PS, while in NaY the presence of high internal electric fields confers to the Cp2Cr molecules a much higher reactivity towards CO. In situ EXAFS data, combined with other spectroscopic techniques and ab initio theoretical calculations, allowed the structural determination of the reaction products and afforded the full comprehension of the complex reactivity of Cp2Cr molecules inside the cavities of PS and NaY hosts.
6. 14th International Conference on X-ray Absorption Fine Structure
Cameriono, Italy
26-31, July, 2009
190
012140-1
012140-6
http://www.iop.org/EJ/abstract/1742-6596/190/1/012140
EXAFS; Organometallic complexes; host-guest chemistry; Cr carbonyls; chromocene; XANES; Heterogeneous catalysis
D. Gianolio; E. Groppo; J. Estephane; C. Prestipino; S. Nikitenko; A. Zecchina; S. Bordiga; M. Taoufik; E. A. Quadrelli; J. M. Basset; C. Lamberti
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/72022
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