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Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os(VI)N–Pt(II) Complex

[Image: see text] Presented herein is a first investigation of the chemical reactivity of osmium-nitrido corroles, which are known for their unusual thermal, chemical, and photochemical stability. Elemental chlorine perchlorinates the β-positions of the triarylcorrole but leaves the OsN unit untouch...

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Autores principales: Reinholdt, Anders, Alemayehu, Abraham B., Gagnon, Kevin J., Bendix, Jesper, Ghosh, Abhik
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7311052/
https://www.ncbi.nlm.nih.gov/pubmed/32227864
http://dx.doi.org/10.1021/acs.inorgchem.0c00654
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author Reinholdt, Anders
Alemayehu, Abraham B.
Gagnon, Kevin J.
Bendix, Jesper
Ghosh, Abhik
author_facet Reinholdt, Anders
Alemayehu, Abraham B.
Gagnon, Kevin J.
Bendix, Jesper
Ghosh, Abhik
author_sort Reinholdt, Anders
collection PubMed
description [Image: see text] Presented herein is a first investigation of the chemical reactivity of osmium-nitrido corroles, which are known for their unusual thermal, chemical, and photochemical stability. Elemental chlorine perchlorinates the β-positions of the triarylcorrole but leaves the OsN unit untouched. The OsN unit is also unaffected by a variety of other electrophilic and nucleophilic reagents. Upon photolysis, however, the anion of Zeise’s salt associates with the nitrido ligand to generate an Os(VI)≡N—Pt(II) complex. The very short OsN–Pt linkage [1.895(9)–1.917(8) Å] and the downfield (195)Pt NMR resonance (−2702 ppm) suggest that the OsN corrole acts as a π-accepting ligand toward the Pt(II) center. This finding represents a rare example of the successful photochemical activation of a metal–ligand multiple bond that is too kinetically inert to exhibit any appreciable reactivity under thermal conditions.
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spelling pubmed-73110522020-06-24 Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os(VI)N–Pt(II) Complex Reinholdt, Anders Alemayehu, Abraham B. Gagnon, Kevin J. Bendix, Jesper Ghosh, Abhik Inorg Chem [Image: see text] Presented herein is a first investigation of the chemical reactivity of osmium-nitrido corroles, which are known for their unusual thermal, chemical, and photochemical stability. Elemental chlorine perchlorinates the β-positions of the triarylcorrole but leaves the OsN unit untouched. The OsN unit is also unaffected by a variety of other electrophilic and nucleophilic reagents. Upon photolysis, however, the anion of Zeise’s salt associates with the nitrido ligand to generate an Os(VI)≡N—Pt(II) complex. The very short OsN–Pt linkage [1.895(9)–1.917(8) Å] and the downfield (195)Pt NMR resonance (−2702 ppm) suggest that the OsN corrole acts as a π-accepting ligand toward the Pt(II) center. This finding represents a rare example of the successful photochemical activation of a metal–ligand multiple bond that is too kinetically inert to exhibit any appreciable reactivity under thermal conditions. American Chemical Society 2020-03-31 2020-04-20 /pmc/articles/PMC7311052/ /pubmed/32227864 http://dx.doi.org/10.1021/acs.inorgchem.0c00654 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Reinholdt, Anders
Alemayehu, Abraham B.
Gagnon, Kevin J.
Bendix, Jesper
Ghosh, Abhik
Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os(VI)N–Pt(II) Complex
title Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os(VI)N–Pt(II) Complex
title_full Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os(VI)N–Pt(II) Complex
title_fullStr Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os(VI)N–Pt(II) Complex
title_full_unstemmed Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os(VI)N–Pt(II) Complex
title_short Electrophilic Activation of Osmium-Nitrido Corroles: The OsN Triple Bond as a π-Acceptor Metallaligand in a Heterobimetallic Os(VI)N–Pt(II) Complex
title_sort electrophilic activation of osmium-nitrido corroles: the osn triple bond as a π-acceptor metallaligand in a heterobimetallic os(vi)n–pt(ii) complex
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7311052/
https://www.ncbi.nlm.nih.gov/pubmed/32227864
http://dx.doi.org/10.1021/acs.inorgchem.0c00654
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