Potassium-controlled synthesis of heterotopic macrocycles based on isothiosemicarbazide

• Published in: Inorganica Chimica Acta 2002-01, Vol.328 (1), p.123-133
• Main Authors: Arion, Vladimir B, Kravtsov, Victor Ch, Gradinaru, Julieta I, Simonov, Yuri A, Gerbeleu, Nicolai V, Lipkowski, Janusz, Wignacourt, Jean-Pierre, Vezin, Hervé, Mentré, Olivier
• Format: Article
• Language: English
• Subjects: Complexes; Copper(II)–potassium; Nickel(II)–potassium; Template; Zinc(II)–potassium
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(01)00717-4

The macrocyclisation reaction of 3,3′-(3,6-dioxaoctane-1,8-diyldioxy)-bis(2-hydroxybenzaldehyde) (1) with S-methylisothiosemicarbazide hydroiodide (H2NNC(SCH3)NH2·HI) in the presence of potassium triflate, followed by addition of M(CH3COO)2·nH2O, where M=Ni, Cu, Zn, afforded [NiLKI3] (2), [NiLK(CF3SO3)] (3), [CuLK(CF3SO3)(CH3OH)] (4) and [(ZnILK)2CH3OH] (5), respectively. Compounds 2–5 have been characterised by X-ray crystallography. IR, electronic, mass, 1H, 13C{1H} and 19F{1H} NMR spectra are reported. Magnetic susceptibility measurements and ESR spectra of 4 indicate weak intermolecular spin–spin interactions, which are mostly dipolar in origin. Starting from the corresponding dialdehyde and S-methylisothiosemicarbazide hydroiodide, in the presence of KCF3SO3 in methanol, followed by addition of M(CH3COO)2·nH2O, where M=Ni, Cu, Zn, the complexes [NiLKI3], [NiLK(CF3SO3)], [CuLK(CF3SO3)(CH3OH)] and [(ZnILK)2CH3OH] have been synthesised. All compounds have been characterised by X-ray crystallography. IR, electronic, mass, 1H and 13C{1H} and 19F{1H} NMR spectra are reported. Magnetic susceptibility measurements and ESR spectra of [CuLK(CF3SO3)(CH3OH)] indicate weak intermolecular spin–spin interactions.