KR-20260063666-A - NITRIL ACTIVATION METHOD OF COBALT HYDROPEROXO COMPLEX WITH ADJUSTED BASICITY

Abstract

The present invention relates to a nitrile activation method of a cobalt hydroperoxo complex with controlled basicity, and can provide a nitrile activation method that forms a cobalt (III)-peroxyimidato complex using a mononuclear cobalt (III)-hydroperoxo complex.

Inventors

• 조재흥
• 손영진

Assignees

• 울산과학기술원

Dates

Publication Date

20260507

Application Date

20241030

Claims (5)

1. Nitrile activation method using a cobalt hydroperoxo complex comprising a compound represented by the following chemical formula 1. [Chemical Formula 1] The above R1 is one selected from alkyl groups having 1 to 10 carbon atoms, and The above R2 is one selected from alkyl groups having 1 to 10 carbon atoms. The above R3 is one selected from a methyl group ( -CH3 ) and a phenyl group (-Ph).
2. In Article 1, The nitrile activation method using the above-mentioned cobalt hydroperoxo complex is a method for nitrile activation of a cobalt hydroperoxo complex achieved through intramolecular nucleophilic attack of a hydroperoxide ligand on a nitrile carbon.
3. In Article 1, The above R1 is a methyl group, and The above R2 is a methyl group, Nitrile activation method using a cobalt hydroperoxo complex.
4. In Article 1, The nitrile activation method using the above-mentioned cobalt hydroperoxo complex is a method of adding a strong Lewis acid to a mononuclear cobalt peroxo complex, Method for nitrile activation of cobalt hydroperoxo complex.
5. In Paragraph 4, The above strong Lewis acid is one or more selected from HOTf (Triflic acid), Al³⁺ , and Sc³⁺ , Method for nitrile activation of cobalt hydroperoxo complex.

Description

NITRIL ACTIVATION METHOD OF COBALT HYDROPEROXO COMPLEX WITH ADJUSTED BASICITY NITRIL ACTIVATION METHOD OF COBALT HYDROPEROXO COMPLEX WITH ADJUSTED BASICITY The present invention relates to a nitrile activation method of a cobalt hydroperoxo complex with controlled basicity. Specifically, it relates to a nitrile activation method for forming a cobalt (III)-peroxyimidato complex using a mononuclear cobalt (III)-hydroperoxo complex. Due to the stability of nitriles with strong C≡N bonds, classical methods for activating nitriles require high energy, and there were problems caused by the demanding reaction conditions. Therefore, research is being conducted on nitrile activation methods under mild conditions compared to existing nitrile activation methods. Figure 1 illustrates the nitrilation reaction of a cobalt (III)-hydroperoxo complex (2) resulting from the reaction of a cobalt (III)-peroxo complex (1) and a nitrile. Figure 2 shows the UV-vis spectrum graph (a), EMI-MS results (b), and H-NMR spectrum graph (c) of a cobalt(III)-peroxo complex in the presence of HOTf (0.25 mM). Figure 3 shows the ORTEP (crystal structure analysis) of the cobalt(III)-peroxo complex. Figure 4 shows the rate constant graph (a), activation parameter graph (b) of the nitrilation reaction of a cobalt hydroperoxo complex, and the correlation graph (c) between the rate constant k and plot (σ) of a para-substituted benzonitrile derivative. Figure 5 shows the rate constant graph (a), activation parameter graph (b), and the correlation graph (c) between the rate constant k and plot (σ) of the para-substituted benzonitrile derivative in the nitrilation reaction of the nitrile derivative. The terms and words used in the specification and claims described below should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define terms to best describe his invention. Therefore, the embodiments described in this specification and the configurations illustrated in the drawings are merely the most preferred embodiments of the present invention and do not represent all of the technical ideas of the present invention; thus, it should be understood that various equivalents and modifications that can replace them may exist at the time of filing this application. Throughout the specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Furthermore, when a part is described as "connected" to another part, this includes not only cases where they are "directly connected" but also cases where they are "electrically connected" with other elements interposed between them. The terms used herein are for describing specific embodiments and are not intended to limit the invention. Terms used in the specification in the singular form may include plural forms unless the context clearly indicates otherwise. Additionally, the terms “comprise” and/or “comprising” used herein specify the presence of the mentioned features, steps, numbers, actions, parts, elements, and/or groups thereof, and do not exclude the presence or addition of one or more other features, steps, numbers, actions, parts, elements, and/or groups thereof. Furthermore, the term "connection" as used in this specification refers not only to the direct connection of certain members but also includes the concept of indirect connection through the interposition of other members between them. Embodiments of the present invention are described below with reference to the attached drawings so that those skilled in the art can easily implement them. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein. Furthermore, in order to clearly explain the present invention in the drawings, parts unrelated to the explanation have been omitted, and similar parts throughout the specification are denoted by similar reference numerals. The present invention can provide a nitrile activation method using a cobalt hydroperoxo complex comprising a compound represented by the following chemical formula 1. [Chemical Formula 1] The above R1 may be one selected from alkyl groups having 1 to 10 carbon atoms. The above R2 may be one selected from alkyl groups having 1 to 10 carbon atoms. The above R3 may be a methyl group ( -CH3 ) or a phenyl group (-Ph). The nitrile activation method using the above-mentioned cobalt hydroperoxo complex may be a method utilizing intramolecular nucleophilic attack of a hydroperoxide ligand on a nitrile carbon. Specifically, the R1 may be a methyl group, an ethyl group, a propyl group, or a butyl group. Preferably, the R1 may be a methyl group ( CH3 ). Specifically, the R2 may be a methyl gro