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Title: Chromocene in porous polystyrene: an example of organometallic chemistry in confined spaces
Authors: Estephane, Jane 
Groppo, Elena
Vitillo, Jenny G.
Damin, Alessandro
Lamberti, Carlo
Bordiga, Silvia
Zecchina, Adriano
Affiliations: Department of Chemical Engineering 
Issue Date: 2009
Part of: Physical chemistry chemical physics
Volume: 11
Issue: 13
Start page: 2218
End page: 2227
In this work, we present an innovative approach to investigate the structure and the reactivity of a molecularly dispersed organometallic compound. The poly(4-ethylstyrene-co-divinylbenzene) microporous system (PS) is used as "solid solvent" able to molecularly disperse CrCp2, allowing: (i) its full characterization by means of spectroscopic techniques; (ii) the pressure and temperature dependent study of its interaction towards simple molecules like CO freely diffusing through the pores; (iii) the accurate determination of the reaction enthalpies by both direct microcalorimetric measurements and by an indirect spectroscopic approach. The experimental results are compared with quantum-mechanical calculations adopting the DFT approximation with two different functionals (namely BP86 and B3-LYP), showing the limitations and the potentialities of DFT methods in predicting the properties of open shell systems. It is concluded that modern DFT methods are able to give a coherent view of the vibrational properties of the CrCp2 molecule (and of the complex formed upon CO adsorption) that well match the experimental results, while the energetic predictions should be taken with care as they are significantly dependent on the functionals used.
Type: Journal Article
Appears in Collections:Department of Chemical Engineering

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