Comparing Metal–Halide and −Oxygen Adducts in Oxidative C/O–H Activation: Au(III)–Cl versus Au(III)–OH

[Image: see text] High-valent metal–halides have come to prominence as highly effective oxidants. A direct comparison of their efficacy against that of traditional metal–oxygen adducts is needed. [Au(III)(Cl)(terpy)](ClO(4))(2) (1; terpy = 2,2′:6′,2-terpyridine) readily oxidized substrates bearing O...

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Autores principales: Lovisari, Marta, Gericke, Robert, Twamley, Brendan, McDonald, Aidan R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8527453/
https://www.ncbi.nlm.nih.gov/pubmed/34582177
http://dx.doi.org/10.1021/acs.inorgchem.1c02222
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author Lovisari, Marta
Gericke, Robert
Twamley, Brendan
McDonald, Aidan R.
author_facet Lovisari, Marta
Gericke, Robert
Twamley, Brendan
McDonald, Aidan R.
author_sort Lovisari, Marta
collection PubMed
description [Image: see text] High-valent metal–halides have come to prominence as highly effective oxidants. A direct comparison of their efficacy against that of traditional metal–oxygen adducts is needed. [Au(III)(Cl)(terpy)](ClO(4))(2) (1; terpy = 2,2′:6′,2-terpyridine) readily oxidized substrates bearing O–H and C–H bonds via a hydrogen atom transfer mechanism. A direct comparison with [Au(III)(OH)(terpy)](ClO(4))(2) (2) showed that 1 was a kinetically superior oxidant with respect to 2 for all substrates tested. We ascribe this to the greater thermodynamic driving force imbued by the Cl ligand versus the OH ligand.
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spelling pubmed-85274532021-10-20 Comparing Metal–Halide and −Oxygen Adducts in Oxidative C/O–H Activation: Au(III)–Cl versus Au(III)–OH Lovisari, Marta Gericke, Robert Twamley, Brendan McDonald, Aidan R. Inorg Chem [Image: see text] High-valent metal–halides have come to prominence as highly effective oxidants. A direct comparison of their efficacy against that of traditional metal–oxygen adducts is needed. [Au(III)(Cl)(terpy)](ClO(4))(2) (1; terpy = 2,2′:6′,2-terpyridine) readily oxidized substrates bearing O–H and C–H bonds via a hydrogen atom transfer mechanism. A direct comparison with [Au(III)(OH)(terpy)](ClO(4))(2) (2) showed that 1 was a kinetically superior oxidant with respect to 2 for all substrates tested. We ascribe this to the greater thermodynamic driving force imbued by the Cl ligand versus the OH ligand. American Chemical Society 2021-09-28 2021-10-18 /pmc/articles/PMC8527453/ /pubmed/34582177 http://dx.doi.org/10.1021/acs.inorgchem.1c02222 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Lovisari, Marta
Gericke, Robert
Twamley, Brendan
McDonald, Aidan R.
Comparing Metal–Halide and −Oxygen Adducts in Oxidative C/O–H Activation: Au(III)–Cl versus Au(III)–OH
title Comparing Metal–Halide and −Oxygen Adducts in Oxidative C/O–H Activation: Au(III)–Cl versus Au(III)–OH
title_full Comparing Metal–Halide and −Oxygen Adducts in Oxidative C/O–H Activation: Au(III)–Cl versus Au(III)–OH
title_fullStr Comparing Metal–Halide and −Oxygen Adducts in Oxidative C/O–H Activation: Au(III)–Cl versus Au(III)–OH
title_full_unstemmed Comparing Metal–Halide and −Oxygen Adducts in Oxidative C/O–H Activation: Au(III)–Cl versus Au(III)–OH
title_short Comparing Metal–Halide and −Oxygen Adducts in Oxidative C/O–H Activation: Au(III)–Cl versus Au(III)–OH
title_sort comparing metal–halide and −oxygen adducts in oxidative c/o–h activation: au(iii)–cl versus au(iii)–oh
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8527453/
https://www.ncbi.nlm.nih.gov/pubmed/34582177
http://dx.doi.org/10.1021/acs.inorgchem.1c02222
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