Cargando…

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...

Descripción completa

Detalles Bibliográficos
Autores principales: Stubbe, Jessica, Suhr, Simon, Beerhues, Julia, Nößler, Maite, Sarkar, Biprajit
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
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
_version_ 1783703776147800064
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
work_keys_str_mv AT stubbejessica thetransformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac
AT suhrsimon thetransformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac
AT beerhuesjulia thetransformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac
AT noßlermaite thetransformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac
AT sarkarbiprajit thetransformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac
AT stubbejessica transformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac
AT suhrsimon transformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac
AT beerhuesjulia transformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac
AT noßlermaite transformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac
AT sarkarbiprajit transformationsofamethylenebridgedbistriazoliumsaltamesoioniccarbenebasedmetallocageandanaloguesoftcneandnacnac