An investigation into the determination of stability constants of metal complexes by convolution-deconvolution cyclic voltammetry

A technique is described for calculating stability constants of metal-ligand complexes from convolution-deconvolution voltammetry. Semi-integration of the cyclic voltammetric currents with respect to time allows calculation of E(1 2 ) values in a manner comparable to the use in polarography of the Heyrovsky-Ilkovic equation. The technique described also allows determination of the ratio of the diffusion coefficients of the free and complexed metal ions and provides a second check of the stoichiometry. A reliable route to the metal-complex stability constants by the equations of Lingane and DeFord and Hume is therefore obtained. Advantages of this technique compared with the use of polarography, differential pulse polarography and pH titrations are discussed, with the complexes formed by cadmium with glycine, alanine, valine and aspartic acid as examples.     

Electron transfer between two silyl-substituted phenylene rings: EPR/ENDOR spectra,DFT calculations,and crystal structure of the one-electron reduction compound of a di(m-silylphenylenedisiloxane)

Reduction of a solution of octamethylcyclo-di(m-silylphenylenedisiloxane) 4 in THF on a potassium mirror leads to EPR/ENDOR spectra characterized by a large coupling (approximately 20 MHz) with two protons, similar to the spectra obtained after reduction of the m-disilylbenzene derivative 5, consistent with a localization of the extra electron on a single ring of 4. The spectra recorded after reduction of 4 at low temperature in the presence of an equimolar amount of 18-crown-6 exhibit couplings of approximately 10 MHz with four protons and indicate that embedding the counterion in crown-ether provokes the delocalization of the unpaired electron on the two phenyl rings of 4. The measured hyperfine interactions agree with those calculated by DFT for the optimized structure of 4(.-). Direct information on the structure of this anion is obtained from the X-ray diffraction of crystals grown at -18 degrees C in reduced solutions containing 4, potassium, and crown ether in a THF/hexane mixture. Both DFT and crystal structures clearly indicate the geometry changes caused by the addition of an electron to 4: the interphenyl distance drastically decreases, leading to a partial overlap of the two rings. The structure of 4(.-) is a model for an electron transfer (ET) transition state between the two aromatic rings. The principal reason for the adoption of this structure lies in the bonding interaction between the LUMO (pi orbitals) of these two fragments; moreover, the constraints of the macrocycle probably contribute to the stabilization of this structure.     

An EPR, ENDOR and EIE study of gamma-irradiated poly (lactide-co-glycolide) polymers

Gamma radiation of poly (lactide-co-glycolide) raw polymers and processed microspheres under vacuum and at 77 K results in the formation of a series of free radicals. The resulting powder electron paramagnetic resonance (EPR) spectrum contains a distribution of several different radicals, depending on the annealing temperature, and is therefore difficult to interpret. By utilising the selectivity of the electron nuclear DOuble resonance (ENDOR) and associated ENDOR induced EPR (EIE) techniques, a more direct approach for the deconvolution of the EPR spectrum can be achieved. Using this approach, the radiolytically induced CH3 *CHC(O)R- chain scission radical was identified at 120 K by simulation of the EIE spectrum. At elevated temperatures (250 K), this radical decays considerably and the more stable radicals -O*CHC(O)-, CH3 *C(OR)C(O)- and CH3 *C(OH)C(O)- predominate. This work demonstrates the utility of the EIE approach to supplement and aid the interpretation of powder EPR spectra of radicals in a polymer matrix.     

Synthesis,DFT calculations,cyclic voltammetry and antibacterial activities of a new blue-violet dye and a new blue-green fluorescent heterocyclic system

The new blue-violet dye 2-(3-hydroxyimino-2,3-dihydroimidazo[1,2-a]pyridin-2-yliden)-2-(2-thienyl)acetonitrile was prepared in high yield from the reaction of 3-nitroimidazo[1,2-a]pyridine with 2-(2-thienyl)acetonitrile by nucleophilic substitution of hydrogen. Acylation of the hydroxyl group led to a new heterocyclic system, (pyrido[2′,1′:2,3] imidazo[4,5-b]thieno[2,3-e]pyridine-11-carbonitrile) with very strong blue-green fluorescent properties. Physical, spectral and analytical data have confirmed the structures of the synthesized dyes. The optical and solvatochromic properties of these compounds were investigated and showed interesting photophysical properties. Density functional theory calculations of blue-violet and fluorescent dyes were performed to provide the optimized geometries, Mulliken atomic charges, relevant frontier orbitals and the prediction of ¹H NMR chemical shifts. The electrochemical properties of these dyes were investigated by cyclic voltammetry and an oxidation wave was observed at a half-wave potential of −0.143 V versus SCE for the blue-violet dye. Also, these new compounds exhibited potent antibacterial activity against Gram positive and negative bacterial species.     

Formation of cross-linked adducts between guanine and thymine mediated by hydroxyl radical and one-electron oxidation: a theoretical study

The role of local geometric and stereo-electronic effects in tuning the preference for different cross-linked adducts between thymine and purinic bases has been analyzed by a computational approach rooted in density functional theory. Our study points out that G--T and T--G tandem lesions are produced according to the same mechanism as A--T and T--A intrastrand adducts, and in both cases purine--T adducts are preferred rather than the opposite sequences. Moreover, use of conceptual DFT tools allows the rationalization of the preferential occurrence of G--T and T--G tandem lesions in place of their A--T and T--A counterparts.     

A kinetic, spectral and theoretical investigation on the role of oxygen in the radiolytic oxidation of a sorbityl cyclic acetal

The oxidation process of the cyclic acetal sorbitylfurfural (SF) has been thoroughly examined from the kinetic, spectroscopic and theoretical point of view. Oxidation has been initiated by the radiolitically produced OH radical in the presence of variable oxygen amounts. Two competing reaction pathways are evidenced which lead to quite different products, although they do not affect the acetal ring integrity. The peroxidation of the hydroxylated furanic ring (k ₄=(6.1±0.9)×10⁸ M⁻¹ s⁻¹) maintains the ring structurevia HO₂^• elimination (k ₆=(1.9±0.4)×10⁵ s⁻¹). Unlike that, the peroxidation of the pseudo-allylic radical (k ₅=(1.9±0.9)×10⁹ M⁻¹ s⁻¹), formedvia β-cleavage, fixes the destructured intermediate, leading to a tetroxide, which slowly decomposes through a Russell mechanism (k ₈=(2.3±0.6)×10² s⁻¹). It is confirmed that the steady state concentration of the tetroxide is very low, which suggests a molar absorption coefficient for it around 1.2×10⁴ M⁻¹ cm⁻¹ at 265 nm. The end products of the latter pathway have been characterized as carboxylic and butenald-sorbitol derivatives. The kinetic and spectral data of every step of the process have been fitted by the above outlined mechanism. The energetics of the mechanism has been detailed byab initio computations as well, carrying further substantiation to it. Semi-empirical calculations were also employed to describe the spectral properties of each intermediate.     

Electrochemical oxidation of 2-pyrimidinethiols and theoretical study of their dimers, disulfides, sulfenyl radicals, and tautomers

The relative energies and structures of 2-pyrimidinethiol (1), 4-methyl-2-pyrimidinethiol (3), 5-methyl-2-pyrimidinethiol (5), and 4,6-dimethylpyrimidinethiol (7), and their dimers, disulfides, sulfenyl radicals, and tautomers have been studied using restricted and unrestricted ab initio theory, density functional theory, complete basis set methods, coupled cluster theory, and quadratic configuration interaction calculations. The electrochemical oxidation of 2-pyrimidinethiol (1), 4-methyl-2-pyrimidinethiol (3), and 4,6-dimethylpyrimidinethiol (7) in ethanenitrile affords the respective disulfides in excellent yields. The less polar 2-pyrimidinethiol tautomers are predicted to be the dominant species in the gas phase. CBS-QB3, CBS-Q, CCD, CCSD(T), QCISD(T), and MP2 predict the energy difference (Erel) between (1) and its tautomer (2-pyrimidinethione, 2) to be in the narrow range from 7.23 to 7.87 kcal/mol. Similar trends are observed in the Erel values for the respective tautomers of 2-pyrimidinethiols (3), (5), and (7). The hybrid density functionals B3LYP, B3P86, B3PW91, and MPW1PW91 predict smaller values for Erel between the tautomers than any of the other models. Substitution of methyl groups at positions 4 and 6 of the pyrimidine ring lowers the energy difference between the respective tautomers while a methyl group at position 5 has little effect. The 2-pyrimidinethiol dimer (13) is predicted to be 5.52 and 4.12 kcal/mol, respectively, lower in energy than the isomeric 2-pyrimidinethione dimer (14) and heterodimer (15). The intramolecular four center transition states (TS1) for the tautomerization of 2-pyrimidinethiols (1, 3a, 3b, 5, and 7) in the gas phase have activation barriers of 34.84, 34.42, 34.02, 35.16, and 33.64 kcal/mol, respectively. Alternative lower energy pathways for tautomerism in the gas phase involve dimers and dimer transition states. Dimers and dimer transition states are also involved in the electrochemical oxidation of the 2-pyrimidinethiols. The APT, Mulliken (MPA), and NBO partial atomic charges are compared with the CHELPG and MKS charges that give the most consistent and similar results.     

The reducibility of Ru,Pt/Ru and Pt oxide electrocatalysts as measured by temperature-programmed reduction and cyclic voltammetry

The electrochemical reduction of alkaline cryptates (222, M)⁺ has been studied on mercury electrode by normal pulse polarography, potentiostatic coulometry and cyclic voltammetry in propylene carbonate as solvent. The corresponding kinetic parameters have been calculated and compared with those obtained on solvated alkaline cations in the same medium. A more detailed study of the electrochemical reduction mechanism of the cryptate (222, K)⁺ shows that the primary product of the reduction is the unstable (222, K^o), and that the final stable products are the free ligand (222) and the amalgam K^o (Hg). The alkaline cations, when complexed by the same (222) ligand, exhibit close values of the polarographic diffusion coefficients. The specific polarographic behaviour of the cryptate (222, Cs)⁺ is described and its stability constant calculated in propylene carbonate. An analytical application of the electrochemical reduction of cryptates is also proposed.     

Stabilization of a subvalent oxidation state of bismuth in N,N-dimethylthioformamide solution: an EXAFS, UV-Vis, IR, and cyclic voltammetry study

At the dissolution of anhydrous bismuth(III) trifluoromethanesulfonate in N,N-dimethylthioformamide (DMTF) a deep red-orange complex, lambda(max) = 457 nm, is formed. Bismuth(III) is reduced by the solvent to a low-valent oxidation state stabilized by the sulfur-coordinating solvent DMTF. The obtained complex is weakly solvated seen by a low EXAFS amplitude and a slightly higher absorption energy of the L(III) edge than of the DMTF-solvated bismuth(III) ion. The EXAFS data reveal a dimeric bismuth complex solvated by a single DMTF molecule, which sulfur atom bridges the bismuth atoms. The Bi-S bond distance is 2.543(2) A, and the Bi...Bi distance is 3.929(7) A giving a Bi-S-Bi angle of 101.2(4) degrees. The very low number of coordinated solvent molecule shows that the lone electron pairs of the reduced bismuth ions are stereochemically active. Cyclic voltammetry investigations provide evidence that at least one bismuth atom in the dimer exists in an oxidation state lower than +III, seen by two peaks at approximately -0.36 and -0.57 V in the reduction half-cycle. The absence of EPR signals excludes the presence of bismuth(II) radicals.     

An investigation of the chromium oxidation state of a monoanionic chromium tris(catecholate) complex by X-ray absorption and EPR spectroscopies

The well-known monoanionic Cr tris(3,5-di-tert-butylcatecholato) complex, [Cr(DTBC)3]-, has been studied by X-ray absorption spectroscopy. The multiple-scattering fit to the XAFS gave good correlation (R = 19.8%) and good values for all of the bond lengths, angles, and Debye-Waller factors. The principal bond lengths and angles around the metal center (Cr-O, 1.96 A; O-C, 1.28 A; O-Cr-O, 81.8 degrees; Cr-O-C, 113.3 degrees) were most consistent with the XRD structure for [Cr(X4C6O2)3]- (X = Cl, Br), compared to those in other oxidation states, [Cr(DTBC)3], [Cr(Cl4C6O2)3], and [Cr(O2C6H4)3]3-. The XANES spectrum shows the main K edge at 6003.3 eV and a preedge peak at 5992.9 eV, which is approximately 8% of the intensity of the main K edge. The XANES data were compared to those for Cr-ehba complexes (ehbaH2 = 2-ethyl-2-hydroxybutanoic acid) of known oxidation states (III, IV, and V) and show, in conjunction with EPR spectroscopy and a reevaluation of XRD structures and theoretical calulations, that the complex is best described as a Cr(V) center with delocalization from the catechol ligands. The [Cr(catecholato)3]n+ (n = 1, 0) complexes have similar EPR spectroscopic and structural properties, respectively, to the 1- complex and are also best described as Cr(V) complexes. Such intermediates are important in the redox reactions of catechol(amine)s, and oxidized amino acids (e.g., DOPA), with carcinogenic Cr(VI) and may have relevance in Cr-induced cancers.     

Coordination stability between metal/ligands interaction by modern spectroscopic studies: IR, electronic, EPR and cyclic voltammetry of cobalt(II) complexes with organic skeleton containing cyclic ligands

A comparative investigation of the interaction of two pyrrole-substituted, mixed oxygen and nitrogen donor, macrocycles ligands have been designed and their coordination interaction with cobalt(II) is studied. Cobalt(II) salts combine with a tetradentate and hexadentate macrocyclic nitrogen/oxygen donor ligands and formed novel cobalt(II) complexes which are characterized by elemental analysis, molar conductance, magnetic moments, mass, (1)H NMR, IR, electronic and EPR spectral studies. At the room temperature magnetic moment for cobalt(II) complexes lie in the range 4.70-5.01BM, which is higher than the spin-only value. All the complexes are high-spin type and have three unpaired electrons. Therefore, the electronic confutation and the splitting of the orbital will be t(2g)(5)eg(2). The electrochemical behaviour of the cobalt(II) complexes, the Co(III)/Co(II) couple are observed. Their positive potential indicates that metal in lower oxidation state is strongly bound to these ligands. The difference between the potential of the anodic peak and cathodic peak remains constant in all complexes. Also, the ratio between the cathodic peak current and square root of the scan rate is practically constant for the studied complexes.     

Inhibition of oxygen reduction on iron phthalocyanine layers by glutathione in buffered neutral media: Investigation by potentiometry,cyclic voltammetry and operational impedance techniques

The inhibition of oxygen reduction on iron—phthalocyanine layers, vacuum sublimed onto a gold surface, has been investigated as a function of various glutathione concentrations. Transient measurements, performed using the operational impedance technique, have shown that specific adsorption of glutathione occurs on the Fe(III) sites. The interpretation of the data by a model of charge carrier injection emphasizes the role of regulation of the electrode activity by glutathione concentrations >0.1 mM.     

Catalytic reduction of acetone by [(bpy)Rh]+: a theoretical mechanistic investigation and insight into cooperativity effects in this system

Lahav, Milstein, and co-workers reported that the complex [(bpy)Rh(hd)](+)PF(6)(-) (bpy = substituted bipyridine ligand, hd = 1,5-hexadiene) shows catalytic activity in the hydrogenation of acetone (T?llner, K. et al. Science 1997, 278, 2100). The activity in an ordered monolayer was found to be dramatically greater than in solution. We used the DFT functional mPW1K (Lynch, B. J. et al. J. Phys. Chem. A 2000, 104, 4811) to investigate the mechanism of the homogenous reaction. The suitability of the mPW1K functional was verified by coupled cluster calculations on a model system. Bulk solvent effects were considered. Various alternative catalytic cycles were evaluated, and we found that one potential mechanism involves metal-catalyzed keto-enol tautomerization to form [(bpy)Rh(enol)](+) that adds hydrogen yielding a complex with axial and equatorial hydride ligands. The reaction continues via transfer of the hydrides to the enolic C=C bond thereby forming 2-propanol and regenerating the catalyst. Another potential catalytic cycle involves formation of [(bpy)Rh(acetone)(2)(H)(2)](+), which has a spectator solvent ligand, and initial transfer of the equatorial hydride to the carbonyl carbon of acetone. Other mechanisms involving hydrogen transfer to the acetone tautomer involved higher barriers. With an eye toward modeling multi-center catalysis, various model systems for the bpy ligand were considered. It was found that diimine (HN=CH-CH=NH) compares very well with bpy, whereas cis-1,2-diiminoethylene (H(2)C=N-CH=CH-N=CH(2)) yields a reaction profile very close to that of bpy. Finally, the system with two rhodium centers, [(diimine)Rh](2)(2+), was investigated. The results strongly suggest that an enol-type catalytic cycle occurs and that cooperativity between the two metal centers is responsible for the acceleration of the reaction in the monolayer system.     

Reaction mechanism of oxidation, hydroxylation, and epoxidation by hypofluorous acid: a theoretical study of unusual H-bond-assisted catalysis

The oxidation of organic molecules by hypofluorous acid (HOF) was studied extensively and systematically by Rozen et al. Therefore, it seems appropriate to refer to the process as Rozen oxidation. An entire set of model molecules was selected for quantum chemical investigation of the oxidation mechanism: a C=C double bond in ethylene, sulfur and selenium in dimethyl derivatives, nitrogen and phosphorus in trimethyl derivatives, as well as methyl azides. In the gas phase, van der Waals complexes between HOF and the previously mentioned species easily are formed, but these complexes are reluctant to undergo oxidation. The addition of another HOF molecule connected with the formation of a cyclic complex (i.e., substrate and two molecules of HOF) seems to be decisive for the oxidation process. The attempt to substitute the second HOF molecule with H2O demonstrated the superiority of HOF. Complexes of this kind decompose along the reaction path smoothly (i.e., with a low activation energy) to the respective oxidation product. A potential role of the hydroxyl cation (HO+) in the oxidation step is mentioned. Besides an oxidation product, one HOF molecule is released (an essential feature of catalysis), and furthermore, hydrogen fluoride is formed. It was suggested by Sertchook et al. (J. Phys. Chem. A 2006, 110, 8275) that the interaction between the substrate to be oxidized and HOF is catalytically influenced by the HF molecule. The mechanism suggested here is more feasible and, particularly at the early stages of the oxidation process, decisive. Also, the role of acetonitrile, used as a solvent by Rozen et al., is discussed in terms of a continuum model. Moreover, passing from potential energies to Gibbs energies is considered.     

An investigation by means of correlation analysis into the mechanisms of oxidation of aryl methyl sulfides and sulfoxides by dimethyldioxirane in various solvents

Relative rate constants have been measured for the oxidation of aryl methyl sulfides and sulfoxides by dimethyldioxirane in acetone, in mixtures of acetone with aprotic co-solvents of both higher and lower relative permittivity, and in aqueous acetone mixtures. Correlation analyses of the effects of substituents in the different solvents show that, with one exception, reactions take place via a single step mechanism in which the formation of the new SO bond and the elimination of acetone occur concertedly. The exception was oxidation of the sulfides in aqueous acetone containing the highest proportion of water of those studied (20% v/v). Here, the behaviour of the reaction is consistent with a two-step mechanism in which the oxidant reversibly attacks the sulfide to form an open-chain sulfonium betaine that subsequently fragments to sulfoxide and acetone. There is no evidence for the participation of an intermediate dioxathietane as has been found in the case of sulfide oxidations by (trifluoromethyl)methyldioxirane in CH(2)Cl(2) and similar aprotic solvents. It is not justified to generalise a mechanism involving a betaine, with or without a derived dioxathietane, to the reactions of dimethyldioxirane in acetone.     

Spectroscopic IR, EPR, and operando DRIFT insights into surface reaction pathways of selective reduction of NO by propene over the Co-BEA zeolite

Interaction of a Co-BEA catalyst with individual components (NO, C(3)H(6), CO, O(2)) and mixtures simulating the real feed of the selective catalytic reduction (SCR) of nitric oxide in static and pulse experiments at variable temperatures was investigated by means of IR, EPR, and operando DRIFT spectroscopy coupled with QMS/GC analysis of the products. Speciation of cobalt active sites into Co(II), mono- and polynuclear oxo-cobalt species as well as CoO clusters was quantified by IR using CO and NO as probe molecules. The key intermediates, by-products, and final products of the SCR reaction were identified and their spectroscopic signatures ascertained. Based on the spectroscopic operando results, a concise mechanistic scheme of the selective catalytic reduction of nitric oxide by propene, triggered by a two-electron Co(II)/Co(0) redox couple, was developed. It consists of a complex network of the sequential/parallel selective reduction steps that are interlocked by the rival nonselective oxidation of the intermediates and their thermal decomposition. It has been shown that the SCR process is initiated by the chemoselective capture of NO from the reaction mixture by the cobalt active sites leading to the cobalt(II) dinitrosyls, which in the excess of oxygen are partially oxidized to surface nitrates and nitrites. N(2)O is produced by semi-decomposition of the dinitrosyl intermediates on the mononuclear centers, whereas NO(2)via NO oxidation on the polynuclear oxo-cobalt sites. Cyanide and isocyanate species, formed together with propene oxygenates in the course of the C=C bond scission, are the mechanistically pivotal reaction intermediates of C(3)H(6) interaction with the dinitrosyles and NO(3)(-)/NO(2)(-) surface species. Dinitrogen is produced by three main reaction routes involving oxidation of cyanides by NO/NO(2), reduction of dinitrosyls, nitrates, and nitrites by propene oxygenates (medium temperature range) or their reduction by carbon monoxide (high temperature range).     

An experimental and theoretical study of molecular structure and vibrational spectra of 3- and 4-pyridineboronic acid molecules by density functional theory calculations

The experimental and theoretical vibrational spectra of 3- and 4-pyridineboronic acids (abbreviated as p3 and p4) were studied. The Fourier transform Raman and Fourier transform infrared spectra of p3 and p4 molecules were recorded in the solid phase. The structural and spectroscopic analysis of the p3 and p4 acids were made by using density functional harmonic calculations. Both p3 and p4 only one form was most stable using B3LYP level with the 6-31G(d), 6-31G(d,p), 6-311G(d), 6-311G(d,p) and 6-311++G(d,p) basis sets. Selected experimental bands were assigned based on the scaled theoretical wavenumbers. Finally, geometric parameters, infrared and Raman bands and intensities were compared with experimental data of the molecules.