Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00584308" target="_blank" >RIV/61388955:_____/24:00584308 - isvavai.cz</a>
Alternative codes found
RIV/61388963:_____/24:00583433
Result on the web
<a href="https://hdl.handle.net/11104/0352239" target="_blank" >https://hdl.handle.net/11104/0352239</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jacs.3c11655" target="_blank" >10.1021/jacs.3c11655</a>
Alternative languages
Result language
angličtina
Original language name
Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction
Original language description
We investigate the electronic structure of aromatic radical anions in the solution phase employing a combination of liquid-jet (LJ) photoelectron (PE) spectroscopy measurements and electronic structure calculations. By using recently developed protocols, we accurately determine the vertical ionization energies of valence electrons of both the solvent and the solute molecules. In particular, we first characterize the pure solvent of tetrahydrofuran (THF) by LJ-PE measurements in conjunction with ab initio molecular dynamics simulations and G(0)W(0) calculations. Next, we determine the electronic structure of neutral naphthalene (Np) and benzophenone (Bp) as well as their radical anion counterparts Np- and Bp(-) in THF. Wherever feasible, we performed orbital assignments of the measured PE features of the aromatic radical anions, with comparisons to UV-vis absorption spectra of the corresponding neutral molecules being instrumental in rationalizing the assignments. Analysis of the electronic structure differences between the neutral species and their anionic counterparts provides understanding of the primarily electrostatic stabilization of the radical anions in solution. Finally, we obtain a very good agreement of the reduction potentials extracted from the present LJ-PES measurements of Np- and Bp(-) in THF with previous electrochemical data from cyclic voltammetry measurements. In this context, we discuss how the choice of solvent holds significant implications for optimizing conditions for the Birch reduction process, wherein aromatic radical anions play crucial roles as reactive intermediates.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA24-10982S" target="_blank" >GA24-10982S: Electrolyte-to-metal transition in the liquid phase: interplay between conductivity and reactivity of alkali-metal ammonia and amine solutions</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of the American Chemical Society
ISSN
0002-7863
e-ISSN
1520-5126
Volume of the periodical
146
Issue of the periodical within the volume
12
Country of publishing house
US - UNITED STATES
Number of pages
15
Pages from-to
8043-8057
UT code for WoS article
001166769300001
EID of the result in the Scopus database
2-s2.0-85185787376