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%2F61388955%3A_____%2F18%3A00497406" target="_blank" >RIV/61388955:_____/18:00497406 - isvavai.cz</a>

Výsledek na webu

<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>

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 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

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 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

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA18-13093S" target="_blank" >GA18-13093S: Katalýza radikálových reakcí polynukleárními centry přechodných kovů v enzymech a biomimetických komplexech</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

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

1521-3773

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