Beyond simple hetero Diels-Alder cycloadditions. A new type of element-ligand cooperativity at N, C,N-coordinated arsinidene and stibinidene centres in the reaction with an electron-deficient alkyne

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F22%3A39919278" target="_blank" >RIV/00216275:25310/22:39919278 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2022/DT/D2DT02499C" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2022/DT/D2DT02499C</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d2dt02499c" target="_blank" >10.1039/d2dt02499c</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Beyond simple hetero Diels-Alder cycloadditions. A new type of element-ligand cooperativity at N, C,N-coordinated arsinidene and stibinidene centres in the reaction with an electron-deficient alkyne

Popis výsledku v původním jazyce

The reactivity of two types of organopnictogen(I) N,C,N-pincer ligand coordinated compound, i.e. [2,6-(DippN=CH)(2)C6H3]E (1-E, where E = As, Sb, Bi; Dipp = 2,6-iPrC(6)H(3)) and [2-(DippN=CH)-6-(DippNHCH(2))C6H3]E (6-E, where E = As or Sb), toward an electron-deficient alkyne, i.e. dimethyl acetylenedicarboxylate (DMAD), is reported. All reactions represent remarkable examples of element-ligand cooperation (ELC). In the first step, all compounds react via dearomatization of a latent heteropnictole ring producing rare examples of hetero Diels-Alder (DA) adducts. These compounds then smoothly convert to 1-arsanaphthalenes via hydrogen migration, thereby recovering the aromatic 10 pi-electron system. Furthermore, in the case of bis(imino) derivatives of 1-E, heating of DA adducts in pyridine led to a hydrogenation of the triple bond of DMAD with the concomitant recovery of the univalent pnictinidene centre, which is in turn able to activate the second molecule of DMAD. In contrast, the non-symmetric derivative of 6-As upon heating in pyridine produced bicyclic trivalent arsenic compounds as a result of an attack of the pendant secondary NH group into the arsa-heterocyclic system. For 6-Sb, a remarkable stoichiometric hydrogenation of the DMAD molecule was observed by NMR spectroscopy involving the reductive elimination of dimethylfumarate in the final step of the reaction sequence. The whole study is accompanied by a theoretical survey that describes the main thermodynamic parameters of the reported reactions and explains the reaction pathways observed in the experiments.

Název v anglickém jazyce

Beyond simple hetero Diels-Alder cycloadditions. A new type of element-ligand cooperativity at N, C,N-coordinated arsinidene and stibinidene centres in the reaction with an electron-deficient alkyne

Popis výsledku anglicky

The reactivity of two types of organopnictogen(I) N,C,N-pincer ligand coordinated compound, i.e. [2,6-(DippN=CH)(2)C6H3]E (1-E, where E = As, Sb, Bi; Dipp = 2,6-iPrC(6)H(3)) and [2-(DippN=CH)-6-(DippNHCH(2))C6H3]E (6-E, where E = As or Sb), toward an electron-deficient alkyne, i.e. dimethyl acetylenedicarboxylate (DMAD), is reported. All reactions represent remarkable examples of element-ligand cooperation (ELC). In the first step, all compounds react via dearomatization of a latent heteropnictole ring producing rare examples of hetero Diels-Alder (DA) adducts. These compounds then smoothly convert to 1-arsanaphthalenes via hydrogen migration, thereby recovering the aromatic 10 pi-electron system. Furthermore, in the case of bis(imino) derivatives of 1-E, heating of DA adducts in pyridine led to a hydrogenation of the triple bond of DMAD with the concomitant recovery of the univalent pnictinidene centre, which is in turn able to activate the second molecule of DMAD. In contrast, the non-symmetric derivative of 6-As upon heating in pyridine produced bicyclic trivalent arsenic compounds as a result of an attack of the pendant secondary NH group into the arsa-heterocyclic system. For 6-Sb, a remarkable stoichiometric hydrogenation of the DMAD molecule was observed by NMR spectroscopy involving the reductive elimination of dimethylfumarate in the final step of the reaction sequence. The whole study is accompanied by a theoretical survey that describes the main thermodynamic parameters of the reported reactions and explains the reaction pathways observed in the experiments.

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

2022

Kód důvěrnosti údajů

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

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

51

Číslo periodika v rámci svazku

41

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

13

Strana od-do

15933-15945

Kód UT WoS článku

000865258300001

EID výsledku v databázi Scopus

2-s2.0-85141016875