High-Valent Ni and Cu Complexes of a Tetraanionic Bis(amidateanilido) Ligand
High-valent metal species are often invoked as intermediates during enzymatic and synthetic catalytic cycles. Anionic donors are often required to stabilize such high-valent states by forming strong bonds with the Lewis acidic metal centers while decreasing their oxidation potentials. In this report, we discuss the synthesis of two high-valent metal complexes [ML]+ in which the NiIII and CuIII centers are ligated by a new tetradentate, tetraanionic bis(amidateanilido) ligand. [ML]+, obtained via chemical oxidation of ML, exhibits UV-vis-NIR, EPR, and XANES spectra characteristic of square planar, high-valent MIII species, suggesting the locus of oxidation for both [ML]+ is predominantly metal-based. This is supported by theoretical analyses, which also support the observed visible transitions as ligand-to-metal charge transfer transitions characteristic of square planar, high-valent MIII species. Notably, [ML]+ can also be obtained via O2 oxidation of ML due to its remarkably negative oxidation potentials (CuL/[CuL]+: -1.16 V, NiL/[NiL]+: -1.01 V vs Fc/Fc+ in MeCN). This demonstrates the exceptionally strong donating nature of the tetraanionic bis(amidateanilido) ligation and its ability to stabilize high-valent metal centers.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:62 |
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| Enthalten in: |
Inorganic chemistry - 62(2023), 37 vom: 18. Sept., Seite 15180-15194 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Nguyen, Bach X [VerfasserIn] |
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| Anmerkungen: |
Date Revised 18.09.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.inorgchem.3c02358 |
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| PPN (Katalog-ID): |
NLM361744315 |
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| 500 | |a Date Revised 18.09.2023 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a High-valent metal species are often invoked as intermediates during enzymatic and synthetic catalytic cycles. Anionic donors are often required to stabilize such high-valent states by forming strong bonds with the Lewis acidic metal centers while decreasing their oxidation potentials. In this report, we discuss the synthesis of two high-valent metal complexes [ML]+ in which the NiIII and CuIII centers are ligated by a new tetradentate, tetraanionic bis(amidateanilido) ligand. [ML]+, obtained via chemical oxidation of ML, exhibits UV-vis-NIR, EPR, and XANES spectra characteristic of square planar, high-valent MIII species, suggesting the locus of oxidation for both [ML]+ is predominantly metal-based. This is supported by theoretical analyses, which also support the observed visible transitions as ligand-to-metal charge transfer transitions characteristic of square planar, high-valent MIII species. Notably, [ML]+ can also be obtained via O2 oxidation of ML due to its remarkably negative oxidation potentials (CuL/[CuL]+: -1.16 V, NiL/[NiL]+: -1.01 V vs Fc/Fc+ in MeCN). This demonstrates the exceptionally strong donating nature of the tetraanionic bis(amidateanilido) ligation and its ability to stabilize high-valent metal centers | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a VandeVen, Warren |e verfasserin |4 aut | |
| 700 | 1 | |a MacNeil, Gregory A |e verfasserin |4 aut | |
| 700 | 1 | |a Zhou, Wen |e verfasserin |4 aut | |
| 700 | 1 | |a Paterson, Alisa R |e verfasserin |4 aut | |
| 700 | 1 | |a Walsby, Charles J |e verfasserin |4 aut | |
| 700 | 1 | |a Chiang, Linus |e verfasserin |4 aut | |
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