Experimentally Calibrated Analysis of the Electronic Structure of CuO+: Implications for Reactivity
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10389384" target="_blank" >RIV/00216208:11310/18:10389384 - isvavai.cz</a>
Result on the web
<a href="https://doi.org/10.1002/anie.201811362" target="_blank" >https://doi.org/10.1002/anie.201811362</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/anie.201811362" target="_blank" >10.1002/anie.201811362</a>
Alternative languages
Result language
angličtina
Original language name
Experimentally Calibrated Analysis of the Electronic Structure of CuO+: Implications for Reactivity
Original language description
The CuO+ core is a central motif of reactive intermediates in copper-catalysed oxidations occurring in nature. The high reactivity of CuO+ stems from a weak bonding between the atoms, which cannot be described by a simple classical model. To obtain the correct picture, we have investigated the acetonitrile-ligated CuO+ ion using neon-tagging photodissociation spectroscopy at 5K. The spectra feature complex vibronic absorption progressions in NIR and visible regions. Employing Franck-Condon analyses, we derived low-lying triplet potential energy surfaces that were further correlated with multireference calculations. This provided insight into the ground and low-lying excited electronic states of the CuO+ unit and elucidated how these states are perturbed by the change in ligation. Thus, we show that the bare CuO+ ion has prevailingly a copper(I)-biradical oxygen character. Increasing the number of ligands coordinated to copper changes the CuO+ character towards the copper(II)-oxyl radical structure.
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
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
—
Continuities
S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Angewandte Chemie - International Edition
ISSN
1433-7851
e-ISSN
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Volume of the periodical
57
Issue of the periodical within the volume
52
Country of publishing house
DE - GERMANY
Number of pages
5
Pages from-to
17053-17057
UT code for WoS article
000454575500018
EID of the result in the Scopus database
2-s2.0-85057885095