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Wavelength-Dependent Photofragmentation and Photoionization of Gaseous (η4-Cycloocta-1,5-diene)(η5-cyclopentadienyl)cobalt
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    Wavelength-Dependent Photofragmentation and Photoionization of Gaseous (η4-Cycloocta-1,5-diene)(η5-cyclopentadienyl)cobalt
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    Department of Chemistry and Biochemistry, University of California at Los Angeles, Los Angeles, California 90095
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2003, 42, 14, 4308–4315
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    https://doi.org/10.1021/ic0300518
    Published June 13, 2003
    Copyright © 2003 American Chemical Society

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    Gas-phase photoreactions and photoproducts of the mixed-ligand compound (η4-cycloocta-1,5-diene)(η5-cyclopentadienyl)cobalt are reported. Significant amounts of the monoligated complexes CoCOD and CoCp are produced, and the relative amounts are wavelength dependent. The COD ligand (with the weakest metal−ligand bonds) is always preferentially labilized as expected, but the relative amounts of the CoCOD and CoCp fragments change by 1 order of magnitude as the excitation wavelength is changed. The gas-phase photoreactions exhibit other surprising features that are uncommon in the photoreactions of organometallic compounds in the gas phase. Significant amounts of the intact cation are formed, in contrast to most reported reactions where fragmentation of the weak metal−ligand bonds precedes ionization. Most surprisingly, fragmentation of the ligands occurs while the ligands are still coordinated. The resulting metal complexes contain ligand fragments that remain coordinated to the metal. Breaking several carbon−carbon bonds with retention of weaker metal−ligand bonds is unexpected. For example, C5H5 undergoes fragmentation while still coordinated to the cobalt, yielding smaller compounds such as Co(CH)+, Co(C2H2)+, Co(C3H3)+, and Co(C4H6)+. Correspondingly, coordinated COD yields Co(C6H6)+, Co(C5H5)+, Co(C4H6)+, Co(C3H3)+, Co(C2H2)+, and Co(CH)+. The wavelength dependence of the ligand labilization is examined by utilizing mass-selected resonance enhanced multiphoton ionization spectroscopy. Both broad bands and sharp lines are observed in the mass-selected excitation spectra. The action spectra obtained in the gas phase while monitoring the cobalt ion follow the absorption onset found in solution. The changes in fragmentation pathways are interpreted in terms of the initially accessed excited state.

    Copyright © 2003 American Chemical Society

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    This article is cited by 12 publications.

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    10. Thomas E. Bitterwolf. Annual review of organometallic and nitrosyl photochemistry: 2003. Coordination Chemistry Reviews 2006, 250 (3-4) , 388-413. https://doi.org/10.1016/j.ccr.2005.10.019
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    12. Sergey Yu. Ketkov *, Heinrich l. Selzle, Edward W. Schlag. Nanosecond multiphoton ionization spectroscopy of transition-metal sandwich compounds: a comparative study of nickelocene, ferrocene and bis(η 6 -benzene)chromium. Molecular Physics 2004, 102 (16-17) , 1749-1757. https://doi.org/10.1080/00268970412331287034

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2003, 42, 14, 4308–4315
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic0300518
    Published June 13, 2003
    Copyright © 2003 American Chemical Society

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