Anionic Rearrangements Following Decarboxylation Of Benzophenone Derivatives With Cryogenic Ir Spectroscopy

Moss, Olivia

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https://hdl.handle.net/2142/116563 Copy

Description

Title

Anionic Rearrangements Following Decarboxylation Of Benzophenone Derivatives With Cryogenic Ir Spectroscopy

Author(s)

Moss, Olivia

Contributor(s)

• Johnson, Mark
• Greis, Kim
• Schleif, Tim
• Rullán Buxó, Anna Gabriella del Rosario
• Perez, Evan H.
• Messinger, Joseph P.

Issue Date

2022-06-22

Keyword(s)

Ions

Abstract

Carbanions are highly reactive intermediates that are commonly used in organic synthesis. Here, we investigate the fundamental gas phase spectroscopy and isomerization of substituted aromatic phenides (deprotonated benzene derivatives) using isomer-selective cryogenic ion vibrational predissociation spectroscopy (1000 \wn – 4200 \wn). The phenide is formed by the decarboxylation of the 4-benzoyl benzoate anion (4BBA$^{–}$, C14H9O3$^{–}$), a substituted benzophenone, in a commercial Orbitrap mass spectrometer before being transferred to the triple focusing time-of-flight photofragmentation mass spectrometer. The resulting spectra are congested, suggesting the presence of multiple isomers. They are revealed by quantum chemical calculations in conjunction with two color IR-IR photobleaching spectroscopy to be the expected phenide, and a new molecule formed by multiple steps of isomerization that end in ring-closed product. The identities of these compounds and the proposed mechanism are confirmed by additional experiments using 4BBA$^{–}$-d$_{9}$ and 2BBA$^{–}$.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Handle URL

https://hdl.handle.net/2142/116563

DOI

https://doi.org/10.15278/isms.2022.WG09

Copyright and License Information

Copyright 2022 held by the authors

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