Chromocene in porous polystyrene: An example of organometallic chemistry in confined spaces

Jane Estephane, Elena Groppo, Jenny G. Vitillo, Alessandro Damin, Carlo Lamberti, Silvia Bordiga, Adriano Zecchina

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

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 CrCp 2 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.

Original languageEnglish (US)
Pages (from-to)2218-2227
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume11
Issue number13
DOIs
StatePublished - Mar 31 2009

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