Copper(II)-Mediated Iodination of 1-Nitroso-2-naphthol |
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| Authors: | Zarina M Efimenko Anton V Rozhkov Vitalii V Suslonov Maxim L Kuznetsov Vadim Yu Kukushkin Nadezhda A Bokach |
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| Institution: | 1.Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034 Saint Petersburg, Russia; (Z.M.E.); (A.V.R.); (V.V.S.); (M.L.K.); (V.Y.K.);2.Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisbon, Portugal;3.Institute of Chemistry and Pharmaceutical Technologies, Altai State University, 656049 Barnaul, Russia |
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| 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. |
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| Keywords: | metal-mediated reaction iodination copper(II) complexes nitrosonaphthol halogen bonding |
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