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 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.

Architecture of Easy-to-Synthesize and Superior Probe Based on Aminoquinoline Appended Naphthoquinone: Instant and On-Site Cu2+ Ion Quantification in Real Samples and Unusual Crystal Structure and Logic Gate Operations

“…Although coordination of one or more nitrate oxygens to the Cu 2+ center was previously observed in literature − regarding similar Cu 2+ containing single crystals, best to our knowledge this is the first Cu 2+ containing dinuclear crystal where the octahedral coordination sphere is fulfilled by the coordination of a naphthoquinone oxygen. All the other angles and bond distances are in close agreement with the literature. − The dihedral angle between the planes formed by naphthoquinone and quinoline moieties is only 8.1° demonstrating the planarity due to the presence of conjugation throughout the whole ligand. The comparison of naked ligand crystal (CCDC 656101) with the complex AQNQ–Cu crystal reveals the elongation of the naphthoquinone CO bond from 1.21 to 1.24 Å due to the weak oxygen coordination to Cu 2+ center.…”