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Copper(II)-Mediated Iodination of 1-Nitroso-2-naphthol.

ABSTRACT: 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)₂·H₂O and 1:2:8 Cu^II/NON/I₂ molar ratio between the reactants. The obtained I-NON was characterized by elemental analyses (C, H, N), high-resolution ESI⁺-MS, ¹H and ¹³C{¹H} NMR, FTIR, UV-vis spectroscopy, TGA, and X-ray crystallography (XRD). The copper(II) complexes bearing deprotonated I-NON were prepared as follows: cis-[Cu(I-NON-H)(I-NON)](I₃) (1) was obtained by the reaction between Cu(NON-H)₂ and I₂ in CHCl₃/MeOH, while trans-[Cu(I-NON-H)₂] (2) was synthesized from I-NON and Cu(OAc)₂ in MeOH. Crystals of trans-[Cu(I-NON-H)₂(THF)₂] (3) and trans-[Cu(I-NON-H)₂(Py)₂] (4) were precipitated from solutions of 2 in CHCl₃/THF and Py/CHCl₃/MeOH mixtures, respectively. The structures of 1 and 3-4 were additionally verified by X-ray crystallography. The characteristic feature of the structures of 1 and 3 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 1 and 3, correspondingly, were studied theoretically at the DFT (PBE0-D3BJ) level using the QTAIM, ESP, ELF, NBO, and IGM methods.

SUBMITTER: Efimenko ZM

PROVIDER: S-EPMC8465374 | biostudies-literature |

REPOSITORIES: biostudies-literature

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