title: Chromocene in porous polystyrene: an example of organometallic chemistry in confined spaces.
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 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.
authors.affiliation: Department of Inorganic, Physical and Materials Chemistry, NIS Centre of Excellence and INSTM Centro di Riferimento, University of Turin, Via P. Giuria 7, I-10125 Torino, Italy.
authors.forename: Jane
authors.initials: J
authors.lastname: Estephane
authors.forename: Elena
authors.initials: E
authors.lastname: Groppo
authors.forename: Jenny G
authors.initials: JG
authors.lastname: Vitillo
authors.forename: Alessandro
authors.initials: A
authors.lastname: Damin
authors.forename: Carlo
authors.initials: C
authors.lastname: Lamberti
authors.forename: Silvia
authors.initials: S
authors.lastname: Bordiga
authors.forename: Adriano
authors.initials: A
authors.lastname: Zecchina
mesh_terms: D000327:Adsorption; D000475:Alkenes / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry; D002857:Chromium / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011137:Polystyrenes / Q000737:chemistry*; D016062:Porosity; D011789:Quantum Theory; D017550:Spectroscopy, Fourier Transform Infrared; D013816:Thermodynamics
chemical_list: D000475:Alkenes; D009942:Organometallic Compounds; D011137:Polystyrenes; D002857:Chromium; D002248:Carbon Monoxide