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

D Gianolio1, E Groppo1, J Estephane2, C Prestipino3, S Nikitenko4, A Zecchina1, S Bordiga1, M Taoufik2, E A Quadrelli2, J M Basset2 and C Lamberti1

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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.


PACS

78.70.Dm X-ray absorption spectra

82.80.Gk Analytical methods involving vibrational spectroscopy

61.66.Hq Organic compounds

81.20.-n Methods of materials synthesis and materials processing

82.65.+r Surface and interface chemistry; heterogeneous catalysis at surfaces

82.30.-b Specific chemical reactions; reaction mechanisms

Subjects

Condensed matter: electrical, magnetic and optical

Surfaces, interfaces and thin films

Condensed matter: structural, mechanical & thermal

Chemical physics and physical chemistry

Dates

Issue 1 (2009)



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