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The transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of TCNE and NacNac
Unusual and unexpected chemical transformations often provide access to completely new types of functional molecules. We report here the synthesis of a methylene-bridged bis-triazolium salt designed as a precursor for a new bis-mesoionic carbene (MIC) ligand. The direct metalation with silver oxide...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179415/ https://www.ncbi.nlm.nih.gov/pubmed/34164084 http://dx.doi.org/10.1039/d0sc06957d |
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author | Stubbe, Jessica Suhr, Simon Beerhues, Julia Nößler, Maite Sarkar, Biprajit |
author_facet | Stubbe, Jessica Suhr, Simon Beerhues, Julia Nößler, Maite Sarkar, Biprajit |
author_sort | Stubbe, Jessica |
collection | PubMed |
description | Unusual and unexpected chemical transformations often provide access to completely new types of functional molecules. We report here the synthesis of a methylene-bridged bis-triazolium salt designed as a precursor for a new bis-mesoionic carbene (MIC) ligand. The direct metalation with silver oxide led to the isolation and crystallographic characterization of a cationic tetranuclear octacarbene–silver(i) complex. During metalation the formal bis-MIC precursor undergoes significant structural changes and chemical transformations. A combined synthetic, crystallographic and (spectro-)electrochemical approach is used to elucidate the mechanistic pathway: starting from the methylene-bridged bis-triazolium salt a single deprotonation leads to a NacNac analogue, which is followed by a redox-induced radical dimerization reaction, generating a new tetra-MIC ligand coordinated to silver(i) central atoms. Decomplexation led to the isolation of the corresponding tetratriazoliumethylene, a profoundly electron-poor alkene, which is an analogue of TCNE. |
format | Online Article Text |
id | pubmed-8179415 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81794152021-06-22 The transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of TCNE and NacNac Stubbe, Jessica Suhr, Simon Beerhues, Julia Nößler, Maite Sarkar, Biprajit Chem Sci Chemistry Unusual and unexpected chemical transformations often provide access to completely new types of functional molecules. We report here the synthesis of a methylene-bridged bis-triazolium salt designed as a precursor for a new bis-mesoionic carbene (MIC) ligand. The direct metalation with silver oxide led to the isolation and crystallographic characterization of a cationic tetranuclear octacarbene–silver(i) complex. During metalation the formal bis-MIC precursor undergoes significant structural changes and chemical transformations. A combined synthetic, crystallographic and (spectro-)electrochemical approach is used to elucidate the mechanistic pathway: starting from the methylene-bridged bis-triazolium salt a single deprotonation leads to a NacNac analogue, which is followed by a redox-induced radical dimerization reaction, generating a new tetra-MIC ligand coordinated to silver(i) central atoms. Decomplexation led to the isolation of the corresponding tetratriazoliumethylene, a profoundly electron-poor alkene, which is an analogue of TCNE. The Royal Society of Chemistry 2021-02-11 /pmc/articles/PMC8179415/ /pubmed/34164084 http://dx.doi.org/10.1039/d0sc06957d Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Stubbe, Jessica Suhr, Simon Beerhues, Julia Nößler, Maite Sarkar, Biprajit The transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of TCNE and NacNac |
title | The transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of TCNE and NacNac |
title_full | The transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of TCNE and NacNac |
title_fullStr | The transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of TCNE and NacNac |
title_full_unstemmed | The transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of TCNE and NacNac |
title_short | The transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of TCNE and NacNac |
title_sort | transformations of a methylene-bridged bis-triazolium salt: a mesoionic carbene based metallocage and analogues of tcne and nacnac |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179415/ https://www.ncbi.nlm.nih.gov/pubmed/34164084 http://dx.doi.org/10.1039/d0sc06957d |
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