Oxidations of N-coordinated Arsinidene and Stibinidene by Substituted Quinones: A Remarkable Follow-Up Reactivity

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F23%3A39920980" target="_blank" >RIV/00216275:25310/23:39920980 - isvavai.cz</a>

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202300018" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cplu.202300018</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cplu.202300018" target="_blank" >10.1002/cplu.202300018</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Oxidations of N-coordinated Arsinidene and Stibinidene by Substituted Quinones: A Remarkable Follow-Up Reactivity

Popis výsledku v původním jazyce

The reactivity of pnictinidenes [2-(DippN=CH)-6-(DippNHCH(2))C6H3]E (where E=As (1) or Sb (2)) toward substituted ortho- and para-quinones is reported. The central pnictogen atom is easily oxidized by ortho-quinones closing five-membered EO2C2 ring. The oxidized antimony derivatives are stable species, while in the case of arsenic compounds the hydrogen of the pendant amino NHCH2 group cleaves one newly formed As-O bonds leading to the closure of a new azaarsole ring. Furthermore, a heating of these arsenic heterocycles resulted in a C-H bond activation at the NCH2 group involved in this heterocycle followed by a reductive elimination of corresponding catechols and arsinidene [2,6-(DippN=CH)C6H3]As. Using of para-quinones, resulted in the oxidation of the central atom with a concomitant hydrogen migration from NHCH2 group even in the case of the antimony derivatives. The reductive elimination of hydroquinones is in this case feasible for all compounds. Studied compounds were characterized by multi-nuclear NMR, IR and Raman spectroscopy and single-crystal X-ray diffraction analysis. The theoretical study focusing the key compounds and reactions is also included.

Název v anglickém jazyce

Oxidations of N-coordinated Arsinidene and Stibinidene by Substituted Quinones: A Remarkable Follow-Up Reactivity

Popis výsledku anglicky

The reactivity of pnictinidenes [2-(DippN=CH)-6-(DippNHCH(2))C6H3]E (where E=As (1) or Sb (2)) toward substituted ortho- and para-quinones is reported. The central pnictogen atom is easily oxidized by ortho-quinones closing five-membered EO2C2 ring. The oxidized antimony derivatives are stable species, while in the case of arsenic compounds the hydrogen of the pendant amino NHCH2 group cleaves one newly formed As-O bonds leading to the closure of a new azaarsole ring. Furthermore, a heating of these arsenic heterocycles resulted in a C-H bond activation at the NCH2 group involved in this heterocycle followed by a reductive elimination of corresponding catechols and arsinidene [2,6-(DippN=CH)C6H3]As. Using of para-quinones, resulted in the oxidation of the central atom with a concomitant hydrogen migration from NHCH2 group even in the case of the antimony derivatives. The reductive elimination of hydroquinones is in this case feasible for all compounds. Studied compounds were characterized by multi-nuclear NMR, IR and Raman spectroscopy and single-crystal X-ray diffraction analysis. The theoretical study focusing the key compounds and reactions is also included.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA21-02964S" target="_blank" >GA21-02964S: Dusíkaté ligandy pro prvky nepřechodných kovů - objemnější, konjugovanější a reaktivnější</a><br>

Návaznosti

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

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

ChemPlusChem

ISSN

2192-6506

e-ISSN

2192-6506

Svazek periodika

88

Číslo periodika v rámci svazku

2

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

"e202300018"

Kód UT WoS článku

000935181600001

EID výsledku v databázi Scopus

2-s2.0-85148609829