Picosecond to millisecond tracking of a photocatalytic decarboxylation reaction provides direct mechanistic insights
Aditi Bhattacherjee (),
Mahima Sneha,
Luke Lewis-Borrell,
Omri Tau,
Ian P. Clark and
Andrew J. Orr-Ewing ()
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Aditi Bhattacherjee: University of Bristol, Cantocks Close
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
Nature Communications, 2019, vol. 10, issue 1, 1-7
Abstract:
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.
Date: 2019
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Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-13154-w
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DOI: 10.1038/s41467-019-13154-w
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