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
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
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
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
<a href="/en/project/GA21-02964S" target="_blank" >GA21-02964S: Nitrogen Ligands for Main-Group Elements - Becoming Bulkier, More Conjugated and Guilty</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Volume of the periodical
51
Issue of the periodical within the volume
41
Country of publishing house
GB - UNITED KINGDOM
Number of pages
13
Pages from-to
15933-15945
UT code for WoS article
000865258300001
EID of the result in the Scopus database
2-s2.0-85141016875