M-O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)-Oxyl and Cobalt(III)-Oxo Complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F19%3A00517294" target="_blank" >RIV/61388955:_____/19:00517294 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/19:10396886

Výsledek na webu

<a href="http://hdl.handle.net/11104/0302605" target="_blank" >http://hdl.handle.net/11104/0302605</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/anie.201904546" target="_blank" >10.1002/anie.201904546</a>

Jazyk výsledku

angličtina

Název v původním jazyce

M-O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)-Oxyl and Cobalt(III)-Oxo Complexes

Popis výsledku v původním jazyce

Terminal oxo complexes of late transition metals are frequently proposed reactive intermediates. However, they are scarcely known beyond Group8. Using mass spectrometry, we prepared and characterized two such complexes: [(N4Py)Co-III(O)](+) (1) and [(N4Py)Co-IV(O)](2+) (2). Infrared photodissociation spectroscopy revealed that the Co-O bond in 1 is rather strong, in accordance with its lack of chemical reactivity. On the contrary, 2 has a very weak Co-O bond characterized by a stretching frequency of <= 659cm(-1). Accordingly, 2 can abstract hydrogen atoms from non-activated secondary alkanes. Previously, this reactivity has only been observed in the gas phase for small, coordinatively unsaturated metal complexes. Multireference ab-initio calculations suggest that 2, formally a cobalt(IV)-oxo complex, is best described as cobalt(III)-oxyl. Our results provide important data on changes to metal-oxo bonding behind the oxo wall and show that cobalt-oxo complexes are promising targets for developing highly active C-H oxidation catalysts.

Název v anglickém jazyce

M-O Bonding Beyond the Oxo Wall: Spectroscopy and Reactivity of Cobalt(III)-Oxyl and Cobalt(III)-Oxo Complexes

Popis výsledku anglicky

Terminal oxo complexes of late transition metals are frequently proposed reactive intermediates. However, they are scarcely known beyond Group8. Using mass spectrometry, we prepared and characterized two such complexes: [(N4Py)Co-III(O)](+) (1) and [(N4Py)Co-IV(O)](2+) (2). Infrared photodissociation spectroscopy revealed that the Co-O bond in 1 is rather strong, in accordance with its lack of chemical reactivity. On the contrary, 2 has a very weak Co-O bond characterized by a stretching frequency of <= 659cm(-1). Accordingly, 2 can abstract hydrogen atoms from non-activated secondary alkanes. Previously, this reactivity has only been observed in the gas phase for small, coordinatively unsaturated metal complexes. Multireference ab-initio calculations suggest that 2, formally a cobalt(IV)-oxo complex, is best described as cobalt(III)-oxyl. Our results provide important data on changes to metal-oxo bonding behind the oxo wall and show that cobalt-oxo complexes are promising targets for developing highly active C-H oxidation catalysts.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

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

58

Číslo periodika v rámci svazku

28

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

6

Strana od-do

9619-9624

Kód UT WoS článku

000476610900051

EID výsledku v databázi Scopus

2-s2.0-85067702360