Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen
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Published:2023-08-23
Issue:17
Volume:28
Page:6206
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ISSN:1420-3049
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Container-title:Molecules
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language:en
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Short-container-title:Molecules
Author:
Fujisawa Kiyoshi1ORCID,
Kataoka Taisei1,
Terashima Kohei1,
Kurihara Haruka1,
de Santis Gonçalves Felipe2,
Lehnert Nicolai2ORCID
Affiliation:
1. Department of Chemistry, Ibaraki University, Mito 310-8512, Ibaraki, Japan
2. Department of Chemistry and Department of Biophysics, University of Michigan, 930 N. University Avenue, Ann Arbor, MI 48109, USA
Abstract
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 3NO−. 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 3NO−, based on spectroscopic and theoretical studies. Unexpectedly, the reaction of [Ni(NO)(I)(L1″)] with O2 yielded [Ni(κ2-O2N)(L1″)2](I3), with the oxidation of both 3NO− and the I− ion to yield NO2− and I3−. Both complexes were characterized by X-ray crystallography, IR, and UV–Vis spectroscopy and theoretical calculations.
Funder
Ibaraki University Priority Research Grant
Joint Usage/Research Center for Catalysis
National Science Foundation
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil
Subject
Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science
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