Cargando…
Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes
The hemilabile P^N ligand MeDalphos enables access to a wide range of stable gold(i) π-complexes with unbiased alkenes and alkynes, as well as electron-rich alkenes and for the first time electron-poor ones. All complexes have been characterized by multi-nuclear NMR spectroscopy and whenever possibl...
Autores principales: | , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8157524/ https://www.ncbi.nlm.nih.gov/pubmed/34084334 http://dx.doi.org/10.1039/c9sc06398f |
_version_ | 1783699700405239808 |
---|---|
author | Navarro, Miquel Toledo, Alberto Mallet-Ladeira, Sonia Sosa Carrizo, E. Daiann Miqueu, Karinne Bourissou, Didier |
author_facet | Navarro, Miquel Toledo, Alberto Mallet-Ladeira, Sonia Sosa Carrizo, E. Daiann Miqueu, Karinne Bourissou, Didier |
author_sort | Navarro, Miquel |
collection | PubMed |
description | The hemilabile P^N ligand MeDalphos enables access to a wide range of stable gold(i) π-complexes with unbiased alkenes and alkynes, as well as electron-rich alkenes and for the first time electron-poor ones. All complexes have been characterized by multi-nuclear NMR spectroscopy and whenever possible, by X-ray diffraction analyses. They all adopt a rare tricoordinate environment around gold(i), with chelation of the P^N ligand and side-on coordination of the alkene, including the electron-rich one, 3,4-dihydro-2H-pyrane. The strength of the N → Au coordination varies significantly in the series. It is the way the P^N ligand accommodates the electronic demand at gold, depending on the alkene. Comparatively, when the chelating P^P ligand (ortho-carboranyl)(PPh(2))(2) is used, gold(i) π-complexes are only isolable with unbiased alkenes. The bonding situation within the gold(i) P^N π-complexes has been thoroughly analyzed by DFT calculations supplemented by Charge Decomposition Analyses (CDA), Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses. Noticeable variations in the donation/back-donation ratio, C[double bond, length as m-dash]C weakening, alkene to gold charge transfer and magnitude of the N → Au coordination were observed. Detailed examination of the descriptors for the Au/alkene interaction and the N → Au coordination actually revealed intimate correlation between the two, with linear response of the MeDalphos ligand to the alkene electronics. The P^N ligand displays non-innocent and adaptative character. The isolated P^N gold(i) π-complexes are reactive and catalytically relevant, as substantiated by the chemo and regio-selective alkylation of indoles. |
format | Online Article Text |
id | pubmed-8157524 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81575242021-06-02 Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes Navarro, Miquel Toledo, Alberto Mallet-Ladeira, Sonia Sosa Carrizo, E. Daiann Miqueu, Karinne Bourissou, Didier Chem Sci Chemistry The hemilabile P^N ligand MeDalphos enables access to a wide range of stable gold(i) π-complexes with unbiased alkenes and alkynes, as well as electron-rich alkenes and for the first time electron-poor ones. All complexes have been characterized by multi-nuclear NMR spectroscopy and whenever possible, by X-ray diffraction analyses. They all adopt a rare tricoordinate environment around gold(i), with chelation of the P^N ligand and side-on coordination of the alkene, including the electron-rich one, 3,4-dihydro-2H-pyrane. The strength of the N → Au coordination varies significantly in the series. It is the way the P^N ligand accommodates the electronic demand at gold, depending on the alkene. Comparatively, when the chelating P^P ligand (ortho-carboranyl)(PPh(2))(2) is used, gold(i) π-complexes are only isolable with unbiased alkenes. The bonding situation within the gold(i) P^N π-complexes has been thoroughly analyzed by DFT calculations supplemented by Charge Decomposition Analyses (CDA), Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses. Noticeable variations in the donation/back-donation ratio, C[double bond, length as m-dash]C weakening, alkene to gold charge transfer and magnitude of the N → Au coordination were observed. Detailed examination of the descriptors for the Au/alkene interaction and the N → Au coordination actually revealed intimate correlation between the two, with linear response of the MeDalphos ligand to the alkene electronics. The P^N ligand displays non-innocent and adaptative character. The isolated P^N gold(i) π-complexes are reactive and catalytically relevant, as substantiated by the chemo and regio-selective alkylation of indoles. The Royal Society of Chemistry 2020-02-04 /pmc/articles/PMC8157524/ /pubmed/34084334 http://dx.doi.org/10.1039/c9sc06398f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Navarro, Miquel Toledo, Alberto Mallet-Ladeira, Sonia Sosa Carrizo, E. Daiann Miqueu, Karinne Bourissou, Didier Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes |
title | Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes |
title_full | Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes |
title_fullStr | Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes |
title_full_unstemmed | Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes |
title_short | Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes |
title_sort | versatility and adaptative behaviour of the p^n chelating ligand medalphos within gold(i) π complexes |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8157524/ https://www.ncbi.nlm.nih.gov/pubmed/34084334 http://dx.doi.org/10.1039/c9sc06398f |
work_keys_str_mv | AT navarromiquel versatilityandadaptativebehaviourofthepnchelatingligandmedalphoswithingoldipcomplexes AT toledoalberto versatilityandadaptativebehaviourofthepnchelatingligandmedalphoswithingoldipcomplexes AT malletladeirasonia versatilityandadaptativebehaviourofthepnchelatingligandmedalphoswithingoldipcomplexes AT sosacarrizoedaiann versatilityandadaptativebehaviourofthepnchelatingligandmedalphoswithingoldipcomplexes AT miqueukarinne versatilityandadaptativebehaviourofthepnchelatingligandmedalphoswithingoldipcomplexes AT bourissoudidier versatilityandadaptativebehaviourofthepnchelatingligandmedalphoswithingoldipcomplexes |