1,2-Diethynylbenzene-Bridged [Cp*(dppe)Fe]n+ Units: Effect of Steric Hindrance on the Chemical and Physical Properties - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2015

1,2-Diethynylbenzene-Bridged [Cp*(dppe)Fe]n+ Units: Effect of Steric Hindrance on the Chemical and Physical Properties

Résumé

The binuclear complex [\Cp*(dppe)Fe-C≡C-\2-μ-(1,2-C6H4)] (o-1) was prepd. via the bis(vinylidene) [\Cp*(dppe)Fe=C=CH-\2-μ-(1,2-C6H4)](PF6)2 (o-1H2(PF6)2) in good yield. The new complex was characterized by ESI-mass spectrometry, IR, multinuclear NMR, and Mossbauer spectroscopies, X-ray diffraction on a single crystal, and cyclic voltammetry. The data are consistent with a strong steric interaction between the vicinal organoiron centers responsible for the very long time of reaction for the prepn. of o-1. The singly and doubly oxidized forms o-1(PF6) and o-1(PF6)2 were prepd. by oxidn. of o-1 with 1 and 2 equiv of ferrocenium salt. These salts were characterized by high-resoln. ESI-mass spectra, XRD analyses on single crystals, and IR, Mossbauer, ESR, UV-vis, and NIR spectroscopies. In addn., the magnetic properties of compd. o-1(PF6)2 were investigated by 1H and 31P NMR. The data were analyzed with the support of quantum chem. calcns. at the DFT level of theory. The radical cation o-1(PF6) belongs to class IIB of the mixed-valence classification (Hab \textless 1500 cm-1). The narrowness of the IVCT bands is explained by the steric hindrance, which limits the no. of conformers. The singlet/triplet states ratio is independent of the temp. for the doubly oxidized complex o-1(PF6)2.

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Chimie
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Dates et versions

hal-01169303 , version 1 (29-06-2015)

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Rim Makhoul, Hiba Sahnoune, Vincent Dorcet, Jean-François Halet, Jean-René Hamon, et al.. 1,2-Diethynylbenzene-Bridged [Cp*(dppe)Fe]n+ Units: Effect of Steric Hindrance on the Chemical and Physical Properties. Organometallics, 2015, 34 (13), pp.3314-3326. ⟨10.1021/acs.organomet.5b00332⟩. ⟨hal-01169303⟩
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