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Initial metal–metal bond breakage detected by fs X-ray scattering in the photolysis of Ru3(CO)12 in cyclohexane at 400 nm

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Abstract

Using femtosecond resolution X-ray solution scattering at a free electron laser we were able to directly observe metal–metal bond cleavage upon photolysis at 400 nm of Ru3(CO)12, a prototype for the photochemistry of transition metal carbonyls. This leads to the known single intermediate Ru3(CO)11(μ-CO)*, with a bridging ligand (μCO) and where the asterisk indicates an open Ru3-ring. This loses a CO ligand on a picosecond time scale yielding a newly observed triple bridge intermediate, Ru3(CO)8(μ-CO)3*. This loses another CO ligand to form the previously observed Ru3(CO)10, which returns to Ru3(CO)12 via the known single-bridge Ru3(CO)10(μ-CO). These results indicate that contrary to long standing hypotheses, metal–metal bond breakage is the only chemical reaction immediately following the photolysis of Ru3(CO)12 at 400 nm. Combined with previous picosecond resolution X-ray scattering data and time resolved infrared spectroscopy these results yield a new mechanism for the photolysis of Ru3(CO)12.

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Author information

Authors and Affiliations

  1. Synchrotron Soleil, L’Orme des Merisiers St Aubin, Gif-sur-Yvette, F-91192, France

    Q. Y. Kong

  2. Department of Physics, Technical University of Denmark, Fysikvej 307, Kongens Lyngby, DK-2800, Denmark

    M. G. Laursen, K. Haldrup, K. S. Kjær, E. Biasin & M. M. Nielsen

  3. European XFEL GmbH, Holzkoppel 4, Schenefeld, D-22869, Germany

    D. Khakhulin

  4. PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, California, 94025, USA

    E. Biasin & K. J. Gaffney

  5. LCLS, SLAC National Accelerator Laboratory, Menlo Park, California, 94025, USA

    T. B. van Driel

  6. European Synchrotron Radiation Facility, Grenoble Cedex, BP 220 F-38043, France

    M. Wulff & V. Kabanova

  7. Ecole Normale Supérieure, PSL Research University, UPMC Univ Paris 06, CNRS, Département de Chimie, PASTEUR, 24 rue Lhomond, Paris, F-75005, France

    R. Vuilleumier

  8. Sorbonne Universités, UPMC Univ Paris 06, ENS, CNRS, PASTEUR, Paris, F-75005, France

    R. Vuilleumier

  9. Sorbonne Universités, UPMC Univ Paris 06, UMR 7600, LPTMC, Paris, F-75005, France

    S. Bratos

  10. Center for High Pressure Science & Technology Advanced Research, 1690 Cailun Rd, Bldg. 6-408, Pudong, Shanghai, 201203, China

    T. C. Weng

  11. European Molecular Biology Laboratory, Hamburg Outstation, EMBL c/o DESY, Notkestrasse 85, Hamburg, D-22603, Germany

    M. H. J. Koch

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  1. Q. Y. Kong
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Corresponding author

Correspondence to T. C. Weng.

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Electronic supplementary information (ESI) available. See DOI: 10.1039/c8pp00420j

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Kong, Q.Y., Laursen, M.G., Haldrup, K. et al. Initial metal–metal bond breakage detected by fs X-ray scattering in the photolysis of Ru3(CO)12 in cyclohexane at 400 nm. Photochem Photobiol Sci 18, 319–327 (2019). https://doi.org/10.1039/c8pp00420j

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