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Picosecond to millisecond tracking of a photocatalytic decarboxylation reaction provides direct mechanistic insights

Author

Listed:
  • Aditi Bhattacherjee

    (University of Bristol, Cantocks Close
    AMOLF)

  • Mahima Sneha

    (University of Bristol, Cantocks Close)

  • Luke Lewis-Borrell

    (University of Bristol, Cantocks Close)

  • Omri Tau

    (University of Bristol, Cantocks Close)

  • Ian P. Clark

    (Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell Oxford)

  • Andrew J. Orr-Ewing

    (University of Bristol, Cantocks Close)

Abstract

The photochemical decarboxylation of carboxylic acids is a versatile route to free radical intermediates for chemical synthesis. However, the sequential nature of this multi-step reaction renders the mechanism challenging to probe. Here, we employ a 100 kHz mid-infrared probe in a transient absorption spectroscopy experiment to track the decarboxylation of cyclohexanecarboxylic acid in acetonitrile-d3 over picosecond to millisecond timescales using a photooxidant pair (phenanthrene and 1,4-dicyanobenzene). Selective excitation of phenanthrene at 256 nm enables a diffusion-limited photoinduced electron transfer to 1,4-dicyanobenzene. A measured time offset in the rise of the CO2 byproduct reports on the lifetime (520 ± 120 ns) of a reactive carboxyl radical in solution, and spectroscopic observation of the carboxyl radical confirm its formation as a reaction intermediate. Precise clocking of the lifetimes of radicals generated in situ by an activated C-C bond fission will pave the way for improving the photocatalytic selectivity and turnover.

Suggested Citation

  • Aditi Bhattacherjee & Mahima Sneha & Luke Lewis-Borrell & Omri Tau & Ian P. Clark & Andrew J. Orr-Ewing, 2019. "Picosecond to millisecond tracking of a photocatalytic decarboxylation reaction provides direct mechanistic insights," Nature Communications, Nature, vol. 10(1), pages 1-7, December.
    • Handle: RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-13154-w
    DOI: 10.1038/s41467-019-13154-w
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