Chryssoula Drouza

Solid state and aqueous solution characterization of rectangular tetranuclear V(IV/V)-p-semiquinonate/hydroquinonate complexes exhibiting a proton induced electron transfer.

Reaction of the non-innocent dinucleating ligand 2,5-bis[N,N-bis(carboxymethyl) aminomethyl]hydroquinone (H 6bicah) with VO (2+) and VO 4 (3-) salts in water in the pH range 2 to 4.5 provides a series of novel tetranuclear V (IV) and/or V (V) macrocycles with the main core consisting of the anions [V (V) 4O 4(mu-O) 2(mu-bicah) 2] (4-) isolated at pH = 2.5 and [V (IV) 2V (V) 2O 4(mu-O) 2(mu-bicas)(mu-bicah)] (5-) and [V (IV) 4O 4(mu-O) 2(mu-bicas) 2] (6-) isolated at pH = 4.5 (bicas (*5-) = 2,5-bis[N,N-bis(carboxymethyl) aminomethyl]- p-semiquinonate), whereas at pH = 2 the dinuclear [(V (IV)O) 2(OH 2) 2(mu-bicah)] (2-) was obtained. All vanadium compounds have been characterized, and the charge of the ligand has been assigned in solid state by X-ray crystallography and infrared spectroscopy. The structures of the tetranuclear anions consist of four vanadium atoms arranged at the corners of a rectangle with the two bridging bicas (*5-) and/or bicah (6-) ligands on the long and the two V (IV/V)-O-V (IV/V) bridges on the short sides of the rectangle. UV-vis, (51)V and (1)H NMR spectroscopy and electrochemistry showed that these complexes interconvert to each other by varying the pH. This pH induced redox transformation of the tetranuclear anions has been attributed to the shift of the reduction potential of the bicas (*5-) to higher values by decreasing the pH. The electron is transferred intramolecularly from the metal ion to the electron accepting semiquinones resulting in reduction of bicas (*5-) to bicah (6-) and concurrent oxidation of the V (IV) to V (V). The resulting complexes are further oxidized by atmospheric oxygen. This system as a model for the H (+) coupled redox reactions in metalloenzymes and its relevance is discussed briefly.

Investigation on uranyl interaction with bioactive ligands. Synthesis and structural studies of the uranyl complexes with glycine and N-(2-mercaptopropionyl)glycine

Summary Three new uranium(VI) compounds have been prepared with glycine (Hgly), N-(2-mercaptopropionyl)glycine (Hmpg) and 2,2′-dithiobis(N-propionylglycine) (tpg). The crystal structure of [UO2(Hgly)2Cl2] has been solved, revealing the uranium atom to be seven-co-ordinated. The two zwitterionic glycines are coordinated to uranium atom by the carboxylate groups, one in a monodentate and the other in a bidentate mode. Solid state studies and low temperature 1H, 13C, 2D COSY and HMQC solution NMR spectra of the [UO2(mpg)(CH3COO)], show that mpg coordinates uranium atom by the carboxylate group.

Synthesis and aqueous solution properties of multinuclear oxo-bridged vanadium(IV/V) complexes.

Reaction of the multifunctional phenolic ligands 2,5-bis[N,N-bis(carboxymethyl)aminomethyl]hydroquinone (H6cahq), 2,2-bis[N,N-bis(carboxymethyl)aminomethyl]-4,4-isopropylidenediphen ol(H6capd),2,2,2-tris[N,N-bis(carboxymethyl)aminomethyl]-1,1 ,1-tris(4-hydroxyphenyl)ethane (H9catp) and the monofunctional 2-[N,N-bis(carboxymethyl)aminomethyl]-4-carboxyphenol (H3cacp), with VOSO4 and NaVO3 affords the oxo-bridged mixed-valence vanadium(IV/V) Na6[(VO)4(mu-O)2(mu-cahq)2] x Na2SO4 x 20H2O (1), HnNa(3-n)[(VO)2(mu-O)(mu-cacp)2] (2), HnNa(3-n)[(VO)4(mu-O)2(mu-capd)2] (3), HnNa(9-n)[(VO)6(mu-O)3(mu3-catp)2] (4). In addition to the synthesis, we report the infrared, magnetic, optical and electrochemical properties of these complexes. The hydrolytic stability at different pH values was also investigated using visible spectroscopy.

Aerial Oxidation of a VIV–Iminopyridine Hydroquinonate Complex: A Trap for the VIV–Semiquinonate Radical Intermediate

The reaction of 2,5-bis[N,N-bis(2-pyridyl-aminomethyl)aminomethyl]-p-hydroquinone (H2bpymah) with VO(2+) salts in acetonitrile or water at a low pH (2.2-3.5) results in the isolation of [{V(IV)(O)(Cl)}2(μ-bpymah)], the p-semiquinonate complex [{V(IV)(O)(Cl)}2(μ-bpymas)](OH), the cyclic mixed-valent hexanuclear compound [{V(V)(O)(μ-O)V(IV)(O)}(μ-bpymah)]3, and [(V(V)O2)2(μ-bpymah)]. [{V(IV)(O)(Cl)}2(μ-bpymas)](OH) is an intermediate of the radical-mediated oxidation of [{V(IV)(O)(Cl)}2(μ-bpymah)] from O2. At lower pH values (2.2), a reversible intramolecular electron transfer from the metal to the ligand of [{V(IV)(O)(Cl)}2(μ-bpymas)](OH) is induced with the concurrent substitution of chlorine atoms by the oxygen-bridging atoms, resulting in the formation of [{V(V)(O)(μ-O)V(IV)(O)}(μ-bpymah)]3. The metal complexes were fully characterized by X-ray crystallography, infrared (IR) spectroscopy, and magnetic measurements in the solid state, as well as by conductivity measurements, UV-vis spectroscopy, and electrochemical measurements in solution. The oxidation states of the metal ions and ligands were determined by the crystallographic data. The [{V(IV)(O)(Cl)}2(μ-bpymah)]-[{V(IV)(O)(Cl)}2(μ-bpymas)](OH) redox process is electrochemically reversible. The V(IV) ion in the semiquinonate compound exhibits a surprisingly low oxophilicity, resulting in the stabilization of OH(-) counterions at acidic pH values. An investigation of the mechanism of this reaction reveals that these complexes induce the reduction of O2 to H2O2, mimicking the activity of enzymes incorporating two redox-active centers (metal-organic) in the active site.

ORGANIC VANADIUM COMPOUNDS-TRANSITION STATE ANALOGY WITH ORGANIC PHOSPHORUS COMPOUNDS

Abstract Vanadium compounds, particularly in oxidation state V, are potent inhibitors of phosphoryl group transfer enzymes. In this paper the existance of a correlation between the coordination geometry of a series of vanadium dipicolinate complexes and their potency as inhibitors for chicken intestinal alkaline phosphatase is examined. We find that within a limited series of vanadium compounds the five-coordinate derivatives are the most potent inhibitors.

PH-potentiometric investigation towards chelating tendencies of p -hydroquinone and phenol iminodiacetate copper(II) complexes

Copper ions in the active sites of several proteins/enzymes interact with phenols and quinones, and this interaction is associated to the reactivity of the enzymes. In this study the speciation of the Cu2+ with iminodiacetic phenolate/hydroquinonate ligands has been examined by pH-potentiometry. The results reveal that the iminodiacetic phenol ligand forms mononuclear complexes with Cu2+ at acidic and alkaline pHs, and a binuclear Ophenolate-bridged complex at pH range from 7 to 8.5. The binucleating hydroquinone ligand forms only 2u2009:u20091 metal to ligand complexes in solution. The pK values of the protonation of the phenolate oxygen of the two ligands are reduced about 2 units after complexation with the metal ion and are close to the pK values for the copper-interacting tyrosine phenol oxygen in copper enzymes.

Synthesis, solution, and structural characterization of tetrahydrofuranyl-2,2-bisphosphonic acid disodium salt

Bisphosphonates are biologically relevant therapeutics for bone disorders and cancer. Reaction of γ-chlorobutyric acid, phosphorus acid, and phosphorus trichloride without the use of solvent gave the tetrahydrofuranyl-2,2-bisphosphonate sodium salt (Na2H2L). The Na2H2L was isolated, characterized in solution by 1H, 13C, and 31P NMR spectroscopy and in solid state by single X-Ray crystallography. The crystal structure showed that the Na2H2L forms in the crystal infinite two-dimensional sheets stacked one parallel to the other. A comparison of the chelating properties of H2L2− with similar hydroxyl bisphosphonate ligands shows that the strength of the Na–O(furanyl/hydroxyl) bond is directly related to the total charge of the ligand anion.

Synthesis, Bonding, and Reactivity of Vanadium(IV) Oxido–Fluorido Compounds with Neutral Chelate Ligands of the General Formula cis-[VIV(═O)(F)(LN–N)2]+

Reaction of the oxidovanadium(IV)-L(N-N) species (L(N-N) is bipy = 2,2-bipyridine or bipy-like molecules) with either BF4(-) or HF and/or KF results in the formation of compounds of the general formula cis-[V(IV)(═O)(F)(L(N-N))2](+). Structural and spectroscopic (electron paramagnetic resonance) characterization shows that these compounds are in the tetravalent oxidation state containing a terminal fluorido ligand. Density functional theory calculations reveal that the V(IV)-F bond is mainly electrostatic, which is reinforced by reactivity studies that demonstrate the nucleophilicity of the fluoride ligand in a halogen exchange reaction and in fluorination of various organic substrates.

σ-Bonded p-Dioxolene Transition Metal Complexes

Metal ions are known to lie in close proximity with these species in biological systems, thus resulting in immediate interaction. The two coupled, metal and organic redox centers have been found to participate in several biological processes such as, the oxidative maintenance of biological amine levels, (Klinman, 1996) tissue (collagen and elastin) formation, (Klinman, 1996) photosynthesis (Calvo, et al., 2000) and respiration (Iwata, et al., 1998). Although the crystal structures of many of these enzymes have been solved, the role of the metal ions in these reactions is still controversial. From another point of view, quinonoid metal complexes exhibit rich redox, magnetic and photochemical properties and thus can underpin key technological advances in the areas of energy storage, sensors, catalysis and “smart materials” (Evangelio & Ruiz-Molina, 2005; Stylianou, et al., 2008). Metal ions interact with hydroquinone systems, through σ-bonding to the oxygen atoms and/or through π-bonding to the carbocyclic ring. The structurally characterized σ-bonded hydroquinone metal complexes are surprisingly limited. Structures of metal ions with psemiquinones and quinones are even rarer, mainly due to the absence of a chelate coordination site in simple p-(hydro/semi)quinone and the low pK values of the semiquinone and quinone oxygen atoms. A strategy to synthesize stable metal complexes with hydroquinone species is to use substituted hydroquinones in o-position with substituents containing one or more donor atoms, enabling in this way the metal atom to

p-Hydroquinone???metal compounds: synthesis and crystal structure of two novel VV???p-hydroquinonate and VIV???p-semiquinonate speciesElectronic supplementary information (ESI) available: Fig. S1: four highest singly occupied molecular orbits (SOMOs) of 1. See http://www.rsc.org/suppdata/cc/b2/b207330g/

Reaction of the p-hydroquinone derivative H2Na4bicah.4H2O with either VIVOSO(4).3H2O and NaVVO3 in equivalent quantities or with NaVVo3 yields the tetranuclear VIVO2+ macrocycle-semiquinonate compound Na6[(VIVO)4-(mu2-O)2[mu2-bicas.(-5)-N,O,O,O]2].Na2SO(4).20H2O (1.Na2SO(4).20H2O) and the dinuclear cis-VVO2(+)-hydroquinone species Na4[(VVO2)2[mu2-bicah(-6)-N,O,O,O]].11H2O (2.11H2O) respectively. Compounds 1.Na2SO(4).20H2O and 2.11H2O were characterized by X-ray structure analysis and ab initio calculations.