Oxidative Addition-Reductive Elimination Supported by a Ligand-Element Cooperation at the Arsinidene and Stibinidene Center
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F25%3A39923306" target="_blank" >RIV/00216275:25310/25:39923306 - isvavai.cz</a>
Result on the web
<a href="https://doi.org/10.1002/chem.202404751" target="_blank" >https://doi.org/10.1002/chem.202404751</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/chem.202404751" target="_blank" >10.1002/chem.202404751</a>
Alternative languages
Result language
angličtina
Original language name
Oxidative Addition-Reductive Elimination Supported by a Ligand-Element Cooperation at the Arsinidene and Stibinidene Center
Original language description
The treatment of pnictinidenes [2-(RNHCH2)-6-(RN=CH)C6H3]E (1As/Sb) (where E=As or Sb) with benzoyl peroxide provided compounds [2-(DippNCH2)-6-(DippN=CH)C6H3]E(O2CPh) (2As/Sb) as a result of two step procedure, i. e. oxidation of the pnictogen centre followed by the elimination of benzoic acid. The reaction between 1As and diphenyl disulfide proceeded in the same vein yielding thiophenol and [2-(DippNCH2)-6-(DippN=CH)C6H3]As(SPh) (3As). Analogous reaction of 1Sb furnished a mixture of [2-(DippNHCH2)-6-(DippN=CH)C6H3]Sb(SPh)2 (3'Sb), [2-(DippNCH2)-6-(DippN=CH)C6H3]Sb(SPh) (3Sb) and PhSH, while NMR studies proved the existence of a dynamic equilibrium between all three compounds in solution and removal of incipient PhSH was necessary for the isolation of 3Sb. Both 1As/Sb smoothly reacted with 2-nitrosotoluene leading to [2-(DippNCH2)-6-(DippN=CH)C6H3]E(O-NH-2-Me-Ph) 4As/Sb and with 4-phenyl-1,2,4-triazoline-3,5-dione giving [2-(DippNCH2)-6-(DippN=CH)C6H3]E[(N(CO)-NH(CO))N-Ph] 5As/Sb. All compounds were characterized by IR, Raman, NMR spectroscopy, and the molecular structures, except for 3As and 5Sb, were determined by single-crystal X-ray diffraction. Furthermore, we scrutinized the thermally induced reductive elimination of benzoic acid and thiophenol from 2-3As/Sb, respectively, and that of 4-phenylurazole from 5As. These eliminations involve C-H activation at the CH2N group, and the recovery of the pnictinidene center in [2,6-(RN=CH)2C6H3]E (6As/Sb). Using DFT calculations a plausible mechanism was suggested for all the investigated reactions, which are in good agreement with the experimental observations.
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
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Chemistry - A European Journal
ISSN
0947-6539
e-ISSN
1521-3765
Volume of the periodical
31
Issue of the periodical within the volume
21
Country of publishing house
DE - GERMANY
Number of pages
9
Pages from-to
"e202404751"
UT code for WoS article
001438697800001
EID of the result in the Scopus database
2-s2.0-105002267573