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Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen

For its important roles in biology, nitrogen monoxide (·NO) has become one of the most studied and fascinating molecules in chemistry. ·NO itself acts as a “noninnocent” or “redox active” ligand to transition metal ions to give metal–NO (M–NO) complexes. Because of this uncertainty due to redox chem...

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Autores principales: Fujisawa, Kiyoshi, Kataoka, Taisei, Terashima, Kohei, Kurihara, Haruka, de Santis Gonçalves, Felipe, Lehnert, Nicolai
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10489029/
https://www.ncbi.nlm.nih.gov/pubmed/37687034
http://dx.doi.org/10.3390/molecules28176206
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author Fujisawa, Kiyoshi
Kataoka, Taisei
Terashima, Kohei
Kurihara, Haruka
de Santis Gonçalves, Felipe
Lehnert, Nicolai
author_facet Fujisawa, Kiyoshi
Kataoka, Taisei
Terashima, Kohei
Kurihara, Haruka
de Santis Gonçalves, Felipe
Lehnert, Nicolai
author_sort Fujisawa, Kiyoshi
collection PubMed
description For its important roles in biology, nitrogen monoxide (·NO) has become one of the most studied and fascinating molecules in chemistry. ·NO itself acts as a “noninnocent” or “redox active” ligand to transition metal ions to give metal–NO (M–NO) complexes. Because of this uncertainty due to redox chemistry, the real description of the electronic structure of the M–NO unit requires extensive spectroscopic and theoretical studies. We previously reported the Ni–NO complex with a hindered N3 type ligand [Ni(NO)(L3)] (L3(−) denotes hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate anion), which contains a high-spin (hs) nickel(II) center and a coordinated (3)NO(−). This complex is very stable toward dioxygen due to steric protection of the nickel(II) center. Here, we report the dioxygen reactivity of a new Ni–NO complex, [Ni(NO)(I)(L1″)], with a less hindered N2 type bis(pyrazolyl)methane ligand, which creates a coordinatively unsaturated ligand environment about the nickel center. Here, L1″ denotes bis(3,5-diisopropyl-1-pyrazolyl)methane. This complex is also described as a hs-nickel(II) center with a bound (3)NO(−), based on spectroscopic and theoretical studies. Unexpectedly, the reaction of [Ni(NO)(I)(L1″)] with O(2) yielded [Ni(κ(2)-O(2)N)(L1″)(2)](I(3)), with the oxidation of both (3)NO(−) and the I(−) ion to yield NO(2)(−) and I(3)(−). Both complexes were characterized by X-ray crystallography, IR, and UV–Vis spectroscopy and theoretical calculations.
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spelling pubmed-104890292023-09-09 Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen Fujisawa, Kiyoshi Kataoka, Taisei Terashima, Kohei Kurihara, Haruka de Santis Gonçalves, Felipe Lehnert, Nicolai Molecules Article For its important roles in biology, nitrogen monoxide (·NO) has become one of the most studied and fascinating molecules in chemistry. ·NO itself acts as a “noninnocent” or “redox active” ligand to transition metal ions to give metal–NO (M–NO) complexes. Because of this uncertainty due to redox chemistry, the real description of the electronic structure of the M–NO unit requires extensive spectroscopic and theoretical studies. We previously reported the Ni–NO complex with a hindered N3 type ligand [Ni(NO)(L3)] (L3(−) denotes hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate anion), which contains a high-spin (hs) nickel(II) center and a coordinated (3)NO(−). This complex is very stable toward dioxygen due to steric protection of the nickel(II) center. Here, we report the dioxygen reactivity of a new Ni–NO complex, [Ni(NO)(I)(L1″)], with a less hindered N2 type bis(pyrazolyl)methane ligand, which creates a coordinatively unsaturated ligand environment about the nickel center. Here, L1″ denotes bis(3,5-diisopropyl-1-pyrazolyl)methane. This complex is also described as a hs-nickel(II) center with a bound (3)NO(−), based on spectroscopic and theoretical studies. Unexpectedly, the reaction of [Ni(NO)(I)(L1″)] with O(2) yielded [Ni(κ(2)-O(2)N)(L1″)(2)](I(3)), with the oxidation of both (3)NO(−) and the I(−) ion to yield NO(2)(−) and I(3)(−). Both complexes were characterized by X-ray crystallography, IR, and UV–Vis spectroscopy and theoretical calculations. MDPI 2023-08-23 /pmc/articles/PMC10489029/ /pubmed/37687034 http://dx.doi.org/10.3390/molecules28176206 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Fujisawa, Kiyoshi
Kataoka, Taisei
Terashima, Kohei
Kurihara, Haruka
de Santis Gonçalves, Felipe
Lehnert, Nicolai
Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen
title Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen
title_full Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen
title_fullStr Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen
title_full_unstemmed Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen
title_short Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen
title_sort coordinatively unsaturated nickel nitroxyl complex: structure, physicochemical properties, and reactivity toward dioxygen
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10489029/
https://www.ncbi.nlm.nih.gov/pubmed/37687034
http://dx.doi.org/10.3390/molecules28176206
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