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Photolytic Generation of Radicals from [η-C5R5Fe+Arene]* Complexes. Implications for Electron Transfer Catalysis and Radical Reactions

  • Chapter
Paramagnetic Organometallic Species in Activation/Selectivity, Catalysis

Part of the book series: NATO ASI Series ((ASIC,volume 257))

Abstract

Visible irradiation of [η-C5R5Fe+Arene] in polar solvents leads to generation of (C5R5)° radicals, (R=H, CH3), which are identified as their spin-trapped adducts. Photophysical studies show that the excited triplet state, a 3 E 1, of these organometallic complexes can be efficiently quenched by classical redox quenchers such as methylviologen or dimethylaniline. The excited state of [η-C5R5Fe+Arene]* complexes can also be quenched by hexamethyl (Dewar) benzene, HMDB. In this case two decay types have been determined: (i) a photochemical path occuring in the excited state surface, where simultaneous regioisomerization of HMDB and photoligand exchange take place, affording the hexamethylbenzene derivative-[η-C5R5Fe + HMB], and (ii) a photoinduced radical chainmechanism (detected on the e.s.r. time scale) for HMDB isomerization, caused by an ET photoprimary process between HMDB (an electron donor molecule) and the [η-C5R5Fe+Arene]* complex. Electrocatalytic studies suggest that in the decay of [η-C5R5Fe+Arene]* complexes, two kinds of transient species (17 or 19 electron) are photogenerated depending on the redox-potentials of the quenchers.

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Authors and Affiliations

  1. Catholic University of Chile Faculty of Chemistry, P.O. BOX 6177, Santiago-Chile, France

    Enrique Roman, Mauricio Barrera & Sergio Hernandez

  2. Institut de Substances Naturelles, CNRS, F-91190, Gif-sur-Yvette, France

    Charles Giannotti

Authors
  1. Enrique Roman
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  2. Mauricio Barrera
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  3. Sergio Hernandez
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  4. Charles Giannotti
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Editors and Affiliations

  1. Faculty of Sciences Saint-Jérôme, Marseille, France

    Michel Chanon , Michel Julliard  & Jean Claude Poite ,  & 

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© 1989 Kluwer Academic Publishers

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Roman, E., Barrera, M., Hernandez, S., Giannotti, C. (1989). Photolytic Generation of Radicals from [η-C5R5Fe+Arene]* Complexes. Implications for Electron Transfer Catalysis and Radical Reactions. In: Chanon, M., Julliard, M., Poite, J.C. (eds) Paramagnetic Organometallic Species in Activation/Selectivity, Catalysis. NATO ASI Series, vol 257. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0877-2_23

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  • DOI: https://doi.org/10.1007/978-94-009-0877-2_23

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-6882-6

  • Online ISBN: 978-94-009-0877-2

  • eBook Packages: Springer Book Archive

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