Correction: Self-assembly of arene ruthenium acylpyrazolone fragments to tetranuclear metallacycles. Molecular structures and solid-state (15)N CPMAS NMR correlations.

Correction for 'Self-assembly of arene ruthenium acylpyrazolone fragments to tetranuclear metallacycles. Molecular structures and solid-state (15)N CPMAS NMR correlations' by Riccardo Pettinari et al., Dalton Trans., 2016, 45, 3974-3982.

Self-assembly of arene ruthenium acylpyrazolone fragments to tetranuclear metallacycles. Molecular structures and solid-state (15)N CPMAS NMR correlations.

Reactions of [(η(6)-cymene)Ru(µ-Cl)Cl]2 with acylpyrazolone ligands HQ' (HQ' in general; in detail, HQ(CH2Cl) = 2-chloro-1-(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)ethanone), HQ(hex) = 1-(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)heptan-1-one), HQ(nPe) = 1-(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-3,3-dimethylbutan-1-one)), in the presence of base, gave the corresponding [(η(6)-cymene)Ru(Q')Cl] mononuclear complexes. They react with AgX (where X = O3SCF3 or BF4) in dry acetone affording cationic metalla-cycles [(η(6)-cymene)Ru(Q')]4(X)4. The complexes were fully characterized by analytical and spectroscopic methods and the solid-state structures of mononuclear and tetranuclear complexes have been determined by single-crystal X-ray diffraction. The hapticity of the acylpyrazolone ligands to the Ru metal centre has also been established by (13)C and (15)N CPMAS NMR spectroscopy for the complexes where the lack of crystallinity prevented the elucidation of the crystal structure by SCXRD data.

Organometallic rhodium(III) and iridium(III) cyclopentadienyl complexes with curcumin and bisdemethoxycurcumin co-ligands.

A series of half-sandwich cyclopentadienyl rhodium(III) and iridium(III) complexes of the type [Cp*M(curc/bdcurc)Cl] and [Cp*M(curc/bdcurc)(PTA)][SO3CF3], in which Cp* = pentamethylcyclopentadienyl, curcH = curcumin and bdcurcH = bisdemethoxycurcumin as O^O-chelating ligands, and PTA = 1,3,5-triaza-7-phosphaadamantane, is described. The X-ray crystal structures of three of the complexes, i.e. [Cp*Rh(curc)(PTA)][SO3CF3] (5), [Cp*Rh(bdcurc)(PTA)][SO3CF3] (6) and [Cp*Ir(bdcurc)(PTA)][SO3CF3] (8), confirm the expected "piano-stool" geometry. With the exception of 5, the complexes are stable under pseudo-physiological conditions and are moderately cytotoxic to human ovarian carcinoma (A2780 and A2780cisR) cells and also to non-tumorigenic human embryonic kidney (HEK293) cells, but lack the cancer cell selectivity observed for related arene ruthenium(II) complexes.

Novel composite plastics containing silver(I) acylpyrazolonato additives display potent antimicrobial activity by contact.

New silver(I) acylpyrazolonato derivatives displaying a mononuclear, polynuclear, or ionic nature, as a function of the ancillary azole ligands used in the synthesis, have been fully characterized by thermal analysis, solution NMR spectroscopy, solid-state IR and NMR spectroscopies, and X-ray diffraction techniques. These derivatives have been embedded in polyethylene (PE) matrix, and the antimicrobial activity of the composite materials has been tested against three bacterial strains (E. coli, P. aeruginosa, and S. aureus): Most of the composites show antimicrobial action comparable to PE embedded with AgNO3 . Tests by contact and release tests for specific migration of silver from PE composites clearly indicate that, at least in the case of the PE, for composites containing polynuclear silver(I) additives, the antimicrobial action is exerted by contact, without release of silver ions. Moreover, PE composites can be re-used several times, displaying the same antimicrobial activity. Membrane permeabilization studies and induced reactive oxygen species (ROS) generation tests confirm the disorganization of bacterial cell membranes. The cytotoxic effect, evaluated in CD34(+) cells by MTT (3-(4,5-dimethylthiazole-2-yl)-2,5-diphenyltetrazoliumbromide) and CFU (colony forming units) assays, indicates that the PE composites do not induce cytotoxicity in human cells. Studies of ecotoxicity, based on the test of Daphnia magna, confirm tolerability of the PE composites by higher organisms and exclude the release of Ag(+) ions in sufficient amounts to affect water environment.