Syntheses, structures and antimicrobial activities of various metal complexes of hinokitiol

Metal–oxygen bonding complexes (M = MgII, MnII, NiII, MoVI, WVI, PdII, SbIII, BiIII, FeIII, TiIV, KI, BaII, ZrIV and HfIV) with a hinokitiol (Hhino; 2-hydroxy-4-isopropylcyclohepta-2,4,6-trienone or β-thujaplicin) ligand, which has two unequivalent oxygen donor atoms, were synthesized and characterized by elemental analysis, TG/DTA, FT-IR and solution (1H and 13C) NMR spectroscopy. Single-crystal X-ray structure analysis revealed various molecular structures for the complexes, which were classified into several families of family, i.e. type A [MII(hino)2(L)]2 (M = MgII, MnII, NiII; L = EtOH or MeOH), with a dimeric structure consisting of one bridging hino− anion, one chelating hino− anion and one alcohol or water molecule, type B, with the octahedral, cis-dioxo, bis-chelate complexes cis-[MVIO2(hino)2] (M = MoVI, WVI), type C, with square planar complex [MII(hino)2] (M = PdII), type D, with tris-chelate, 7-coordinate complexes with one inert electron pair [MIII(hino)3] (M = SbIII, BiIII), type D′, with the bis-chelate, pseudo-6-coordinate complexes with one inert electron pair [MIII(hino)2X] (M = SbIII, X = Br), type E, with tris-chelate, 6-coordinate complexes with Δ and Λ isomers [MIII(hino)3] (M = FeIII), type E′ of bis-chelate, 6-coordinate complex [MIV(hino)2X2] (M = TiIV, X = Cl), type F, with water-soluble alkali metal salts [MI(hino)] (M = KI), and type H, with tetrakis-chelate, 8-coordinate complexes [MIV(hino)4](M = ZrIV, HfIV). These structural features were compared with those of metal complexes with a related ligand, tropolone (Htrop). The antimicrobial activities of these complexes, evaluated in terms of minimum inhibitory concentration (MIC; μg mL−1) in two systems, were compared to elucidate the relationship between structure and antimicrobial activity.

Several metal complexes with hinokitiol were synthesized and characterized by elemental analysis, TG/DTA, FT-IR and solution NMR spectroscopy. Single-crystal X-ray analyses of eight hinokitiolato–metal complexes were performed. According to the structural studies including reported ones, hinokitiolato–metal complexes were classified into eight families. Antimicrobial activities of these analytically pure metal complexes were evaluated in terms of the minimum inhibitory concentration in two systems.Figure optionsDownload as PowerPoint slide