Journal article

Publication year: 2017

Pages: 9573-9576

Journal: Angewandte Chemie

Volume number: 129

Issue number: 32

DOI Link: https://doi.org/10.1002/ange.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, 129(32), pp. 9573-9576. https://doi.org/10.1002/ange.201705140

APA Citation style: Gerbig, D., & Schreiner, P. (2017). Formation of a Tunneling Product in the Photorearrangement of o‐Nitrobenzaldehyde. Angewandte Chemie. 129(32), 9573-9576. https://doi.org/10.1002/ange.201705140