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%2F61388955%3A_____%2F18%3A00497406" target="_blank" >RIV/61388955:_____/18:00497406 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1002/anie.201811362" target="_blank" >http://dx.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 5 K. 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.n
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
<a href="/en/project/GA18-13093S" target="_blank" >GA18-13093S: Radical catalysis of enzymatic and biomimetic polynuclear transition-metal active sites</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
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
1521-3773
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