Experimentally Calibrated Analysis of the Electronic Structure of CuO+: Implications for Reactivity

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Experimentally Calibrated Analysis of the Electronic Structure of CuO+: Implications for Reactivity

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Experimentally Calibrated Analysis of the Electronic Structure of CuO+: Implications for Reactivity

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Angewandte Chemie - International Edition

ISSN

1433-7851

e-ISSN

—

Svazek periodika

57

Číslo periodika v rámci svazku

52

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

5

Strana od-do

17053-17057

Kód UT WoS článku

000454575500018

EID výsledku v databázi Scopus

2-s2.0-85057885095