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Title: A multitechnique approach to spin-flips for Cp 2Cr(II) chemistry in confined state
Authors: Estephane, Jane 
Groppo, Elena
vitillo J, M
Kervern, G
Damin, Alessandro
Gianolio, Diego
Lamberti, Carlo
Bordiga, Silvia
Quadrelli, Alessandra Elsje
Basset, Jean Marie
Emsley, L
Pintacuda, G
Zecchina, Adriano
Affiliations: Department of Chemical Engineering 
Issue Date: 2010
Part of: Journal of physical chemistry C
Volume: 114
Issue: 10
Start page: 4451
End page: 4458
Paramagnetic solid-state NMR, extended X-ray absorption fine structure (EXAFS), and Raman spectroscopies, along with detailed quantum mechanical calculations performed with different density functional theory (DFT) functionals, are successfully applied to investigate the magnetic, structural, and vibrational properties of molecularly isolated chromocene (Cp2Cr, where Cp = C5H5) and of its Cp2Cr(CO) adduct. Paramagnetic solid-state NMR unequivocally demonstrates that a spin flip occurs by coming from the paramagnetic Cp2Cr (triplet state) to the diamagnetic Cp2Cr(CO) adduct (singlet state), thus clarifying the theoretical dilemma of the disagreement among different functionals in predicting the most stable spin state. EXAFS and Raman spectroscopies are able to experimentally discriminate between singlet and triplet states, because a different spin state corresponds to a different geometry of the molecule, and therefore to different vibrational features. The here reported multitechnique approach could have great relevance in establishing the occurrence of spin flip in the chemical reactivity of transition metal complexes in both homo- and heterogeneous catalysis.
DOI: 10.1021/jp907986w
Open URL: Link to full text
Type: Journal Article
Appears in Collections:Department of Chemical Engineering

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