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Photochemistry of Metal-Metal Bonded Carbonyls and its Relationship to Electron Transfer Chain Catalysis

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Photoprocesses in Transition Metal Complexes, Biosystems and Other Molecules. Experiment and Theory

Part of the book series: NATO ASI Series ((ASIC,volume 376))

Abstract

Irradiation of the complexes (CO)5MnMn(CO)3(α-diimine) into their visible absorption band gives rise to homolysis of the metal-metal bond and release of CO from the Mn(CO)3(α-diimine) moiety. Only the homolysis reaction leads to product formation at room temperature, loss of CO is the only reaction observed at low temperatures. The radicals formed by the homolysis reaction undergo very interesting radical coupling and electron transfer (chain) reactions. The mechanisms of these reactions are discussed and attention is paid to the character of the excited state from which the reactions take place. The corresponding halide complexes Mn(CO)3(bpy)X show a similar formation of Mn(CO)3(bpy) radicals. Preliminary m.o. data of Mn(CO)3(bpy)X (X=C1,I) and resonance Raman spectra obtained for Re(CO)3(PTol-DAB)Br confirm the presence of a lowest LLCT state for these halide complexes.

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Authors and Affiliations

  1. Anorganisch Chemisch Laboratorium, University of Amsterdam, Nieuwe Achtergracht 166, Amsterdam, The Netherlands, 1018 WV

    D. J. Stufkens, T. v.d. Graaf, G. J. Stor & A. Oskam

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  1. D. J. Stufkens
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  2. T. v.d. Graaf
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  3. G. J. Stor
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  4. A. Oskam
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Editors and Affiliations

  1. Laboratoire de Chimie Théorique Institut de Chimie, Université Louis Pasteur, 1, rue Blaise Pascal, BP 296, 67008, Strasbourg, France

    Elise Kochanski (Director) (Director)

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Stufkens, D.J., v.d. Graaf, T., Stor, G.J., Oskam, A. (1992). Photochemistry of Metal-Metal Bonded Carbonyls and its Relationship to Electron Transfer Chain Catalysis. In: Kochanski, E. (eds) Photoprocesses in Transition Metal Complexes, Biosystems and Other Molecules. Experiment and Theory. NATO ASI Series, vol 376. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-2698-4_9

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  • DOI: https://doi.org/10.1007/978-94-011-2698-4_9

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-5195-8

  • Online ISBN: 978-94-011-2698-4

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