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Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates

We report the synthesis and the reactivity of 1,2,3‐triazolin‐5‐imine type mesoionic imines (MIIs). The MIIs are accessible by a base‐mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O‐stretching freque...

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Autores principales: Rudolf, Richard, Neuman, Nicolás I., Walter, Robert R. M., Ringenberg, Mark. R., Sarkar, Biprajit
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9322014/
https://www.ncbi.nlm.nih.gov/pubmed/35286004
http://dx.doi.org/10.1002/anie.202200653
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author Rudolf, Richard
Neuman, Nicolás I.
Walter, Robert R. M.
Ringenberg, Mark. R.
Sarkar, Biprajit
author_facet Rudolf, Richard
Neuman, Nicolás I.
Walter, Robert R. M.
Ringenberg, Mark. R.
Sarkar, Biprajit
author_sort Rudolf, Richard
collection PubMed
description We report the synthesis and the reactivity of 1,2,3‐triazolin‐5‐imine type mesoionic imines (MIIs). The MIIs are accessible by a base‐mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O‐stretching frequencies in MII−CO(2) and −Rh(CO)(2)Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N‐heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituent‐induced fluorine‐specific interactions and undergo C−H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO–LUMO gap compared to other related ligands. MIIs are potentially able to act as both π‐donor and π‐acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development.
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spelling pubmed-93220142022-07-30 Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates Rudolf, Richard Neuman, Nicolás I. Walter, Robert R. M. Ringenberg, Mark. R. Sarkar, Biprajit Angew Chem Int Ed Engl Research Articles We report the synthesis and the reactivity of 1,2,3‐triazolin‐5‐imine type mesoionic imines (MIIs). The MIIs are accessible by a base‐mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O‐stretching frequencies in MII−CO(2) and −Rh(CO)(2)Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N‐heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituent‐induced fluorine‐specific interactions and undergo C−H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO–LUMO gap compared to other related ligands. MIIs are potentially able to act as both π‐donor and π‐acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development. John Wiley and Sons Inc. 2022-04-19 2022-06-20 /pmc/articles/PMC9322014/ /pubmed/35286004 http://dx.doi.org/10.1002/anie.202200653 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Rudolf, Richard
Neuman, Nicolás I.
Walter, Robert R. M.
Ringenberg, Mark. R.
Sarkar, Biprajit
Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title_full Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title_fullStr Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title_full_unstemmed Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title_short Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
title_sort mesoionic imines (miis): strong donors and versatile ligands for transition metals and main group substrates
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9322014/
https://www.ncbi.nlm.nih.gov/pubmed/35286004
http://dx.doi.org/10.1002/anie.202200653
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