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. 2021 Sep 21;26(18):5708.
doi: 10.3390/molecules26185708.

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

Zarina M Efimenko  1 , Anton V Rozhkov  1 , Vitalii V Suslonov  1 , Maxim L Kuznetsov  1   2 , Vadim Yu Kukushkin  1   3 , Nadezhda A Bokach  1
Affiliations

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

Zarina M Efimenko et al. Molecules. .

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 CuII/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.

Keywords: copper(II) complexes; halogen bonding; iodination; metal-mediated reaction; nitrosonaphthol.

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Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Scheme 1
Scheme 1
Synthesis of I-NON via CuII-mediated iodination of NON.
Figure 1
Figure 1
View of the molecular structure of I-NON obtained from XRD study. Nonhydrogen atoms are given as probability ellipsoids of atomic displacements (p = 0.5).
Figure 2
Figure 2
View of the molecular structure of 1 obtained from XRD study. Nonhydrogen atoms are given as probability ellipsoids of atomic displacements (p = 0.5).
Figure 3
Figure 3
View of the molecular structure of 3 obtained from XRD study. Only one from two symmetrical, independent molecules 3 is given for the sake of simplicity. Nonhydrogen atoms are given as probability ellipsoids of atomic displacements (p = 0.5).
Figure 4
Figure 4
View of the molecular structure of 4 obtained from XRD study. Nonhydrogen atoms are given as probability ellipsoids of atomic displacements (p = 0.5).
Figure 5
Figure 5
Computational models.
Figure 6
Figure 6
Contour line diagram of the Laplacian distribution ∇2ρ(r), selected bond paths, zero flux surfaces (A,C,E) and the sign(λ2)ρ(r) function mapped on the δginter isosurface of 0.005 a.u. and blue-cyan-green-yellow-red color scale −0.02 < sign(λ2)ρ(r) < 0.02 for the I···I and I···O contacts (B,D,F) for BM11 (A,B), BM12 (C,D) and BM31 (E,F).
Figure 7
Figure 7
ESP distribution mapped on the 1.1× van der Waals surface for M1 (A) and ELF for BM12 (B).
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