Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents

N‐containing molecules are mostly derived from ammonia (NH(3)). Ammonia activation has been demonstrated for single transition metal centers as well as for low‐valent main group species. Phosphinidenes, mono‐valent phosphorus species, can be stabilized by phosphines, giving so‐called phosphanylidene...

Descripción completa

Detalles Bibliográficos
Autores principales: Dankert, Fabian, Siewert, Jan‐Erik, Gupta, Priyanka, Weigend, Florian, Hering‐Junghans, Christian
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9400956/
https://www.ncbi.nlm.nih.gov/pubmed/35594171
http://dx.doi.org/10.1002/anie.202207064
_version_ 1784772859330035712
author Dankert, Fabian
Siewert, Jan‐Erik
Gupta, Priyanka
Weigend, Florian
Hering‐Junghans, Christian
author_facet Dankert, Fabian
Siewert, Jan‐Erik
Gupta, Priyanka
Weigend, Florian
Hering‐Junghans, Christian
author_sort Dankert, Fabian
collection PubMed
description N‐containing molecules are mostly derived from ammonia (NH(3)). Ammonia activation has been demonstrated for single transition metal centers as well as for low‐valent main group species. Phosphinidenes, mono‐valent phosphorus species, can be stabilized by phosphines, giving so‐called phosphanylidenephosphoranes of the type RP(PR′(3)). We demonstrate the facile, metal‐free NH(3) activation using ArP(PMe(3)), affording for the first time isolable secondary aminophosphines ArP(H)NH(2). DFT studies reveal that two molecules of NH(3) act in concert to facilitate an NH(3) for PMe(3) exchange. Furthermore, H(2)NR and HNR(2) activation is demonstrated.
format Online
Article
Text
id pubmed-9400956
institution National Center for Biotechnology Information
language English
publishDate 2022
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-94009562022-08-26 Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents Dankert, Fabian Siewert, Jan‐Erik Gupta, Priyanka Weigend, Florian Hering‐Junghans, Christian Angew Chem Int Ed Engl Communications N‐containing molecules are mostly derived from ammonia (NH(3)). Ammonia activation has been demonstrated for single transition metal centers as well as for low‐valent main group species. Phosphinidenes, mono‐valent phosphorus species, can be stabilized by phosphines, giving so‐called phosphanylidenephosphoranes of the type RP(PR′(3)). We demonstrate the facile, metal‐free NH(3) activation using ArP(PMe(3)), affording for the first time isolable secondary aminophosphines ArP(H)NH(2). DFT studies reveal that two molecules of NH(3) act in concert to facilitate an NH(3) for PMe(3) exchange. Furthermore, H(2)NR and HNR(2) activation is demonstrated. John Wiley and Sons Inc. 2022-07-04 2022-08-08 /pmc/articles/PMC9400956/ /pubmed/35594171 http://dx.doi.org/10.1002/anie.202207064 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Communications
Dankert, Fabian
Siewert, Jan‐Erik
Gupta, Priyanka
Weigend, Florian
Hering‐Junghans, Christian
Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents
title Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents
title_full Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents
title_fullStr Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents
title_full_unstemmed Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents
title_short Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents
title_sort metal‐free n−h bond activation by phospha‐wittig reagents
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9400956/
https://www.ncbi.nlm.nih.gov/pubmed/35594171
http://dx.doi.org/10.1002/anie.202207064
work_keys_str_mv AT dankertfabian metalfreenhbondactivationbyphosphawittigreagents
AT siewertjanerik metalfreenhbondactivationbyphosphawittigreagents
AT guptapriyanka metalfreenhbondactivationbyphosphawittigreagents
AT weigendflorian metalfreenhbondactivationbyphosphawittigreagents
AT heringjunghanschristian metalfreenhbondactivationbyphosphawittigreagents

Ejemplares similares