Despina Hatzipanayioti

Electrochemical and spectroscopic studies of 2,3-dihydroxybenzoic acid, its oxidation products and their interaction with manganese(II), in dimethyl sulfoxide solutions

The electrochemical and spectroscopic behaviour of 2,3-dihydroxybenzoic acid (2,3-DHBA) and its oxidized forms have been studied in dimethyl sulfoxide solutions under aerobic and anaerobic conditions. The products resulting from the reaction with manganese(II) (in dimethyl sulfoxide) are also studied by cyclic voltammetry, u.v–vis., n.m.r. and e.s.r. spectroscopies. Under anaerobic conditions the anions of the ligand form stable complexes with manganese(II) and (III) of MnL2 type, while in the presence of air the oxidized forms of the ligand react with manganese(II) to give mixed-valence species. The chemical stability of the semiquinone and its manganese complexes in addition to its photosensitivity is noteworthy. Calculations show that the electrogenerated manganese(III)–(2,3-DHB–semiquinone) system is stable, but redox-active and can undergo a two-electron exchange (per monomer). The dimeric (or oligomeric) species should be good candidates for water oxidation studies.

Interaction of Ni(II) with 2,3-dihydroxybenzoic acid

Abstract The reaction of NiCl 2 ·6H 2 O with 2,3-dihydroxybenzoic acid=L in n -PrOH:H 2 O=1:1 solution, produced the complex {[Ni 5 L 5 (OH) 7 ]K 4 ·13H 2 O} n . Its structure was investigated using elemental analysis, IR, UV–Vis, NMR and ES MS spectroscopy. The complex is unstable in aqueous solution and its decomposition scheme was proposed on the basis of NMR and ES MS spectra. This may contribute to the understanding of oxidative degradation of catecholic derivatives by Ni(II), as well as to other similar ones.

Theoretical and experimental investigation of the semiquinone forms of protocatechuic acid. The effect of manganese.

Ten oxidized, oxygenated and dimeric forms of protocatechuic acid (PCA, 3,4-dihydroxybenzoic acid, 3,4-DHBA) have been studied using DFT calculations (at the B3LYP/TZVP level of theory) and their structural and spectroscopic parameters (electronic transitions, NMR resonances) have been calculated. Combination with experimental results (under anaerobic or aerobic environment) determines the conditions for the existence of protonated, fully deprotonate and/or oxygenated semiquinones of PCA. Several energy optimized conformers containing manganese-(PCA-semiquinones) and water or/and peroxo-groups have been drawn (species 11-16) and their structural and spectroscopic properties have been calculated at the same level of theory. Experimental parallel to the theoretical results provide evidence for the existence of Mn(II)- and Mn(III)-[PCA-semiquinone] as well the conditions of dioxygen activation. Two of the blue solids (17 and 18) isolated from these solutions, have been characterized. Elemental analyzes, TGA, IR and ESR spectra support the formulation Mn(2)(PCA)(2)(O(2))(OH)(2)(AcO)(ClO(4))(2)(H(2)O)(3) (17), and Mn(2)(PCA)(2)(O(2))(2)(OH)(2)(AcO)H(2)O (18). Their ESR spectra, in solution (blue solutions), are almost identical and indicative of Mn(IV) existence. From the whole investigation, the activation of dioxygen by the PCA, its relocation on manganese and the oxidation of the metal ion have been provided.

The chemistry and preparation of tantalum complexes with 2,3-dihydroxy benzoic acid: Experimental and theoretical investigation

The effect of 2,3-dihydroxybenzoic acid (2,3DHBA, pyrocatechuic acid) on the chloro-alkoxo-species [TaCl(5-x)(OMe)(x)], formed by dissolving TaCl(5) in MeOH, has been studied. The coordination of 2,3DHBA-H(2)(-) on Ta (V) replacing MeO-terminal groups was monitored via NMR spectroscopy. The yellow solid 1 was isolated from the mixture of TaCl(5), with neutral 2,3-DHBA, in MeOH. From this solid the elemental (C, H and Ta), the thermogravimetric analyses, the IR, NMR, ESR and electronic spectra support the formula Ta(2)(2,3DHBA)(2)(O)(2)Cl(4)(MeO)(4). The ESR spectrum of solid 1, at 4.2 K, shows a half-field signal apart from a multiline signal around g=2, supporting evidence for semiquinone and Ta (IV) presence. The occurrence of superoxide radical, in the low temperature of ESR spectrum recording, cannot be ruled out. By heating the solid 1 at 500°C, an oxide phase showing porous character (SEM) and retaining CO(2) (IR), is evident. Solid 1 heated at 900°C, leads to the formation of β-Ta(2)O(5) orthorhombic phase, as the XRD pattern indicates. The hydrolytic process of solid 1, in aqueous solutions, has been studied; the presence of paramagnetic species generated in situ upon addition of base and the consequent degradative process of 2,3-DHBA, under aerobic conditions is obvious. In order to gain information for the structure of solid 1, DFT calculations have been performed for some theoretical models, based on the empirical formula of solid 1. The calculated structural and spectroscopic parameters have been correlated to experimental results. The energy optimized structures may give an idea about the way of MeCl and MeOMe formation as well some possible intermediates of the hydrolytic mechanism.

Vanadium reactions with 3,4–dihydroxyphenylethanoic acid in alcohol solutions. Aromatic ring degradation

The reaction of Vv with 3,4–dihydroxyphenylethanoic acid (3,4–DHPE) was studied by various spectroscopic techniques. Vanadium-catechol complexation is the first step, and is followed by stepwise ligand degradation, leading to several products, including AcOH. The mechanism of this degradation is investigated.

Theoretical and experimental investigation of the oxidized and oxygenated forms of pyrocatechuic acid (2,3-dihydroxybenzoic acid)

The catecholic derivative 2,3-dihydroxybenzoic acid (2,3-DHBA or pyrocatechuic acid) represents a diversity of actions in enzymatic processes. In the present study DFT calculations (at the B3LYP/TZVP level of theory) have been performed for neutral 2,3DHBA and its dimer (models 1-1a), several semiquinone forms of 2,3-DHBA, namely the neutral (models 2-4), the monoionized (models 5-7), the di-ionized (models 8) and the dimer 7a. The more stable species in each case are those with the carboxyl group protonated. Oxygenated adducts were also constructed (models 10-15) in which the dioxygen is either H-bonded to the catecholic or carboxylic hydrogen or it is concerned to act on the intradiol or extradiol carbon atoms. The side-on placement of O(2) on C(2) facilitates the intradiol C-C cleavage. Protonation of the oxygenated on C(1) adduct leads to decarboxylation of 2,3-DHBA. Isolation in the solid state and characterization by ESMS, IR, NMR, electronic spectra of the blue-green oxidized product of 2,3-DHBA (solid 1) supports the possibility of the existence of the semiquinone form or the hydroperoxide-adduct. Experimental spectroscopic data are correlated to the calculated spectroscopic parameters. In the ESMS the decarboxylation and degradation products as well a peroxo-adduct have been detected. Oxygenated species may also account for the plethora of redox signals in the cyclic voltammograms of solid 1 (in DMSO solutions).

Preparation, spectroscopic and high field NMR relaxometry studies of gadolinium(III) complexes with the asymmetric tetraamine 1,4,7,11-tetraazaundecane

The reaction of Gd(III) with asymmetric tetramine 1,4,7,11-tetraazaundecane (2,2,3-tet, L(1)) ligand has been studied via NMR spectroscopy. The ligand proton longitudinal relaxation rates (R(1)) have been used to estimate the distances of these protons from the Gd(III) center, in Gd(III)-L(1) reaction solutions, in H(2)O/D(2)O 5/1 mixtures. Two Gd(III) complexes [Gd(III)(L(1))(NH(3))(H(2)O)(4)](CH(3)COO)(3)*2H(2)O (1) and [Gd(III)(L(1))(NH(3))(H(2)O)(2)]Cl(3)*EtOH (2) have been isolated and characterized by elemental analyses, TGA, IR, NMR and relaxometry measurements. The NMR relaxation measurements of 2 in aqueous solutions have been performed, under various temperature or concentration conditions, and compared with those of the commercial contrast agents Gd(III)-DTPA and Gd(III)-DTPA-BMA. It has also been studied the influence of (i) the Gd(III) inner-sphere water molecule number (q) alteration and (ii) the steric constraint enhancement on the metal site, over the relaxation rate values of the parent aqueous solution of Gd(III)-2,2,3-tet, and of the aqueous solutions of 2.