Journal article

Publication year: 2017

Pages: 9445-9448

Journal: Angewandte Chemie International Edition

Volume number: 56

Issue number: 32

DOI Link: https://doi.org/10.1002/anie.201705140

Publisher: Wiley

Abstract: 

The photochemical rearrangement of o‐nitrobenzaldehyde to o‐nitrosobenzoic acid, first reported in 1901, has been shown to proceed via a distinct ketene intermediate. In the course of matrix isolation experiments in various host materials at temperatures as low as 3 K, the ketene was re‐investigated in its electronic and vibrational ground states. It was shown that hitherto unreported H‐tunneling dominates its reactivity, with half‐lives of a few minutes. Unexpectedly, the tunneling product is different from o‐nitrosobenzoic acid formed in the photoprocess: Once prepared by irradiation, the ketene spontaneously rearranges to an isoxazolone via an intriguing mechanism initiated by H‐tunneling. CCSD(T)/cc‐pVTZ computations reveal that this isoxazolone is neither thermodynamically nor kinetically favored under the experimental conditions, and that formation of this unique tunneling product constitutes a remarkable and new example of tunneling control.

Harvard Citation style: Gerbig, D. and Schreiner, P. (2017) Formation of a Tunneling Product in the Photorearrangement of o‐Nitrobenzaldehyde, Angewandte Chemie International Edition, 56(32), pp. 9445-9448. https://doi.org/10.1002/anie.201705140

APA Citation style: Gerbig, D., & Schreiner, P. (2017). Formation of a Tunneling Product in the Photorearrangement of o‐Nitrobenzaldehyde. Angewandte Chemie International Edition. 56(32), 9445-9448. https://doi.org/10.1002/anie.201705140