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Enhanced Catalytic Activity of Nickel Complexes of an Adaptive Diphosphine–Benzophenone Ligand in Alkyne Cyclotrimerization
[Image: see text] Adaptive ligands, which can adapt their coordination mode to the electronic structure of various catalytic intermediates, offer the potential to develop improved homogeneous catalysts in terms of activity and selectivity. 2,2′-Diphosphinobenzophenones have previously been shown to...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2019
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6400243/ https://www.ncbi.nlm.nih.gov/pubmed/30854242 http://dx.doi.org/10.1021/acscatal.8b05025 |
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author | Orsino, Alessio F. Gutiérrez del Campo, Manuel Lutz, Martin Moret, Marc-Etienne |
author_facet | Orsino, Alessio F. Gutiérrez del Campo, Manuel Lutz, Martin Moret, Marc-Etienne |
author_sort | Orsino, Alessio F. |
collection | PubMed |
description | [Image: see text] Adaptive ligands, which can adapt their coordination mode to the electronic structure of various catalytic intermediates, offer the potential to develop improved homogeneous catalysts in terms of activity and selectivity. 2,2′-Diphosphinobenzophenones have previously been shown to act as adaptive ligands, the central ketone moiety preferentially coordinating reduced metal centers. Herein, the utility of this scaffold in nickel-catalyzed alkyne cyclotrimerization is investigated. The complex [((p-tol)L1)Ni(BPI)] ((p-tol)L1 = 2,2′-bis(di(para-tolyl)phosphino)-benzophenone; BPI = benzophenone imine) is an active catalyst in the [2 + 2 + 2] cyclotrimerization of terminal alkynes, selectively affording 1,2,4-substituted benzenes from terminal alkynes. In particular, this catalyst outperforms closely related bi- and tridentate phosphine-based Ni catalysts. This suggests a reaction pathway involving a hemilabile interaction of the C=O unit with the nickel center. This is further borne out by a comparative study of the observed resting states and DFT calculations. |
format | Online Article Text |
id | pubmed-6400243 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-64002432019-03-06 Enhanced Catalytic Activity of Nickel Complexes of an Adaptive Diphosphine–Benzophenone Ligand in Alkyne Cyclotrimerization Orsino, Alessio F. Gutiérrez del Campo, Manuel Lutz, Martin Moret, Marc-Etienne ACS Catal [Image: see text] Adaptive ligands, which can adapt their coordination mode to the electronic structure of various catalytic intermediates, offer the potential to develop improved homogeneous catalysts in terms of activity and selectivity. 2,2′-Diphosphinobenzophenones have previously been shown to act as adaptive ligands, the central ketone moiety preferentially coordinating reduced metal centers. Herein, the utility of this scaffold in nickel-catalyzed alkyne cyclotrimerization is investigated. The complex [((p-tol)L1)Ni(BPI)] ((p-tol)L1 = 2,2′-bis(di(para-tolyl)phosphino)-benzophenone; BPI = benzophenone imine) is an active catalyst in the [2 + 2 + 2] cyclotrimerization of terminal alkynes, selectively affording 1,2,4-substituted benzenes from terminal alkynes. In particular, this catalyst outperforms closely related bi- and tridentate phosphine-based Ni catalysts. This suggests a reaction pathway involving a hemilabile interaction of the C=O unit with the nickel center. This is further borne out by a comparative study of the observed resting states and DFT calculations. American Chemical Society 2019-01-31 2019-03-01 /pmc/articles/PMC6400243/ /pubmed/30854242 http://dx.doi.org/10.1021/acscatal.8b05025 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes. |
spellingShingle | Orsino, Alessio F. Gutiérrez del Campo, Manuel Lutz, Martin Moret, Marc-Etienne Enhanced Catalytic Activity of Nickel Complexes of an Adaptive Diphosphine–Benzophenone Ligand in Alkyne Cyclotrimerization |
title | Enhanced Catalytic
Activity of Nickel Complexes of an Adaptive Diphosphine–Benzophenone
Ligand in Alkyne Cyclotrimerization |
title_full | Enhanced Catalytic
Activity of Nickel Complexes of an Adaptive Diphosphine–Benzophenone
Ligand in Alkyne Cyclotrimerization |
title_fullStr | Enhanced Catalytic
Activity of Nickel Complexes of an Adaptive Diphosphine–Benzophenone
Ligand in Alkyne Cyclotrimerization |
title_full_unstemmed | Enhanced Catalytic
Activity of Nickel Complexes of an Adaptive Diphosphine–Benzophenone
Ligand in Alkyne Cyclotrimerization |
title_short | Enhanced Catalytic
Activity of Nickel Complexes of an Adaptive Diphosphine–Benzophenone
Ligand in Alkyne Cyclotrimerization |
title_sort | enhanced catalytic
activity of nickel complexes of an adaptive diphosphine–benzophenone
ligand in alkyne cyclotrimerization |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6400243/ https://www.ncbi.nlm.nih.gov/pubmed/30854242 http://dx.doi.org/10.1021/acscatal.8b05025 |
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