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Photochemistry of Organo-metal Carbonyls: Stereochemical and Catalytic Aspects

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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

Multiple photosubstitution of CO ligands in Group 8 and Group 6 transition metal carbonyls is investigated in the context of photocatalytic processes, such as olefin isomerization and diene hydrogenation or hydrosilylation. Emphasis is placed on four topics. (i) Quantum yields and photokinetics: the photochemical conversion of Fe(CO)5′ Ru(CO)5′ and W(CO)6 into multi-substituted derivatives (using trimethyl phosphite and/or E-cyclooctene as the incoming ligand) is monitored by means of quantitative IR-spectroscopy; quantum yields for the individual steps are evaluated on the basis of the appropriate photokinetic formalism, which accounts for mutual internal light filtering and includes both consecutive and parallel reactions, if necessary. (ii) M3(CO)12 (Fe, Ru, Os) cluster photochemistry. (iii) Catalytic aspects: as specific examples, the Fe(CO)3 and the Cr(CO)3 groups are recognized as the repeating units in the catalytic cycles of alkene isomerization and diene hydrogenation or hydrosilylation, respectively; photogenerated labile complexes containing the respective M(CO)3 units are employed as reservoir complexes for investigating the catalytic processes separated from the photo-induction period. (iv) Structure and bonding: the single-faced π-acceptor character of olefin ligands is the key factor, which governs the structures and stabilities of olefin-substituted metal carbonyls in the trigonal-bipyramidal (d8) and octahedral (d6) geometries and, thus, largely determines the catalytic activities of such compounds; for mechanistic studies on labile type olefin complexes advantage is taken of the exceptional coordination properties of E-cyclooctene, which is quite a unique olefin in this respect.

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  1. Max-Planck-Institut für Strahlenchemie, Stiftstraße 34-36, Mülheim an der Ruhr, Germany, D-4330

    F.-W. Grevels

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  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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Grevels, FW. (1992). Photochemistry of Organo-metal Carbonyls: Stereochemical and Catalytic Aspects. 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_7

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