Ana Foi

Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands

Two mononuclear MnIII complexes [Mn(3,5-F2salpn)(H2O)2][B(C6H5)4]·2H2O (1·2H2O) and [Mn(3,5-Cl2salpn)(OAc)(H2O)]·H2O (2·H2O), where H2salpn=1,3-bis(salicylidenamino)propane, have been prepared and characterized. The crystal structure of 1·H2O shows that this complex forms μ-aqua dimers with a short Mn⋯Mn distance of 4.93Å. Under anaerobic conditions, the two complexes are stable in solution and possess trans-diaxial symmetry with the tetradentate Schiff base ligand symmetrically arranged in the equatorial plane. When left in air, these complexes slowly dimerize to yield high-valent [MnIV2(3,5-X2-salpn)2(μ-O)2] in which each X2-salpn ligand wraps the two Mn ions. This process is favored in basic medium where the deprotonation of the bound water molecule is concomitant with air oxidation. The two complexes catalyze the dismutation of superoxide (superoxide dismutase (SOD) activity) and peroxide (catalase (CAT) activity) in basic medium. The phenyl-ring substituents play an important role on the CAT reaction but have little effect on SOD activity. Kinetics and spectroscopic results indicate that 1 and 2 catalyze H2O2 disproportionation through a cycle involving MnIII2 and MnIV2 dimers, unlike related complexes with a more rigid and smaller chelate ring, which employ MnIII/MnVO monomers.

N-butylpyridinium undecachlorocarbadodecaborate and comparison with similar compounds.

The title compound, C(9)H(14)N(+)·CHB(11)Cl(11)(-), was obtained in the course of our continuing studies of the low-melting salts of closo- and nido-carborane cage anions with alkylpyridinium and dialkylimidazolium cations. The title compound is the first example of a pyridinium salt of a perchlorinated carborane anion. The structure consists of one N-butylpyridinium cation counterbalanced by one perchlorinated carborane cage anion per asymmetric unit. By changing the counter-ion, different packings are observed, and to try to understand this the new structure is compared with five similar compounds.

Chloro-bis-(naphthalen-1-yl)phosphane.

In the title compound, C20H14ClP, the dihedral angle between the naphthyl rings is 81.77 (6)°. The crystal packing suggests weak π–π stacking interactions between the naphthyl rings in adjacent units [minimum ring centroid separation 3.7625 (13) Å].

5-Hy-droxy-3-methyl-5-phenyl-4,5-di-hydro-1H-pyrazole-1-carbothio-amide.

In the title compound C11H13N3OS, the aromatic ring and the dihydropyrazole ring are oriented orthogonally with respect to each other, making a dihedral angle of 89.92 (9)°. An intramolecular O—H⋯S hydrogen bond occurs. In the crystal, weak N—H⋯N and N—H⋯S hydrogen bonds link the molecules into a columnar stack propagating along the b axis.