Copper(II)-Mediated Iodination of 1-Nitroso-2-naphthol
oleh: Zarina M. Efimenko, Anton V. Rozhkov, Vitalii V. Suslonov, Maxim L. Kuznetsov, Vadim Yu. Kukushkin, Nadezhda A. Bokach
| Format: | Article |
|---|---|
| Diterbitkan: | MDPI AG 2021-09-01 |
Deskripsi
The 3-Iodo-1-nitrosonaphthalene-2-ol (I-NON) was obtained by the copper(II)-mediated iodination of 1-nitroso-2-naphthol (NON). The suitable reactants and optimized reaction conditions, providing 94% NMR yield of I-NON, included the usage of Cu(OAc)<sub>2</sub>·H<sub>2</sub>O and 1:2:8 Cu<sup>II</sup>/NON/I<sub>2</sub> molar ratio between the reactants. The obtained I-NON was characterized by elemental analyses (C, H, N), high-resolution ESI<sup>+</sup>-MS, <sup>1</sup>H and <sup>13</sup>C{<sup>1</sup>H} NMR, FTIR, UV-vis spectroscopy, TGA, and X-ray crystallography (XRD). The copper(II) complexes bearing deprotonated I-NON were prepared as follows: <i>cis</i>-[Cu(I-NON–H)(I-NON)](I<sub>3</sub>) (<b>1</b>) was obtained by the reaction between Cu(NON-H)<sub>2</sub> and I<sub>2</sub> in CHCl<sub>3</sub>/MeOH, while <i>trans</i>-[Cu(I-NON–H)<sub>2</sub>] (<b>2</b>) was synthesized from I-NON and Cu(OAc)<sub>2</sub> in MeOH. Crystals of <i>trans</i>-[Cu(I-NON–H)<sub>2</sub>(THF)<sub>2</sub>] (<b>3</b>) and <i>trans</i>-[Cu(I-NON–H)<sub>2</sub>(Py)<sub>2</sub>] (<b>4</b>) were precipitated from solutions of <b>2</b> in CHCl<sub>3</sub>/THF and Py/CHCl<sub>3</sub>/MeOH mixtures, respectively. The structures of <b>1</b> and <b>3</b>–<b>4</b> were additionally verified by X-ray crystallography. The characteristic feature of the structures of <b>1</b> and <b>3</b> is the presence of intermolecular halogen bonds with the involvement of the iodine center of the metal-bound deprotonated I-NON. The nature of the I···I and I···O contacts in the structures of <b>1</b> and <b>3</b>, correspondingly, were studied theoretically at the DFT (PBE0-D3BJ) level using the QTAIM, ESP, ELF, NBO, and IGM methods.