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Gábor Lente

Publications and source records attributed to Gábor Lente.

15 recordsLinked to original sources
PubMed2006

Stochastic analysis of the parity-violating energy differences between enantiomers and its implications for the origin of biological chirality.

A stochastic description of a racemic mixture is developed taking into account the slight energy difference between enantiomers originating from parity violation (DeltaE(PV) approximately equal to 10(-13) Jmol(-1)). The system can be described by an asymmetric binomial distribution. A method is developed to calculate the probability of forming the more-stable isomer in excess, which is not significantly larger than 50% under normal conditions. It is concluded that the parity-violating energy difference between enantiomers is very unlikely to be relevant in considerations about the origin of biological chirality.

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PubMed2005

Stochastic kinetic models of chiral autocatalysis: a general tool for the quantitative interpretation of total asymmetric synthesis.

A continuous time discrete state stochastic kinetic approach is used to study various chiral autocatalytic models in which the possibility of total asymmetric synthesis arises. It is shown that this approach is superior to the deterministic approaches used earlier and is able to interpret many aspects of chiral autocatalysis. First-order autocatalysis, independently of further kinetic details of the system, leads to a unique final statistical distribution of enantiomers. Higher order autocatalysis, on the other hand, leads to a final state where one of the enantiomers is in overwhelming excess over the other. Criteria are postulated to differentiate between inherently stochastic phenomena in chiral autocatalytic reactions and irreproducibility because of insufficient control of external factors.

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PubMed2005

Kinetics of the light-driven aqueous autoxidation of sulfur(IV) in the absence and presence of iron(II).

The photochemical autoxidation of aqueous, acidic sulfur(IV) solutions was studied in the absence and presence of iron(II) by a newly introduced technique using a diode-array spectrophotometer, in which the same light source is used to drive and detect the reaction. Based on detailed kinetic and stoichiometric data sets, a non-chain mechanism is proposed for the autoxidation of sulfur(IV). In this mechanism, excited hydrated sulfur dioxide, *H2O.SO2, first reacts with O2 to form peroxomonosulfate ion, HSO5-, which rapidly oxidizes another H2O.SO2 to give hydrogensulfate ion as a final product. In the presence of iron(II), the formation of iron(III) was detected, which can be interpreted through the simultaneous contribution of two additional pathways: some of the HSO5- formed oxidizes iron(II) instead of sulfur(iv), and *H2O.SO2 also reacts directly with iron(II) to yield iron(III). This mechanism provides a sufficient quantitative interpretation of all experimental observations.

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PubMed2005

Highly efficient photoinitiation in the cerium(III)-catalyzed aqueous autoxidation of sulfur(IV). An example of comprehensive evaluation of photoinduced chain reactions.

The photoinitiated and cerium(III)-catalyzed aqueous reaction between sulfite ion and oxygen has been studied in a diode-array spectrophotometer using the same light beam for excitation and detection. Cerium(III) is identified as the photoactive absorbing species, and the production of cerium(IV) initiates a radical chain reaction. To interpret all the experimental findings, a simple scheme is proposed, in which the additional chain carriers are sulfite ion radical (SO3(-.)), sulfate ion radical (SO4(-.), and peroxomonosulfate ion radical (SO5(-.). The overall rate of oxidation is proportional to the square root of the light intensity per unit volume, which is readily interpreted by the second-order termination reaction of the proposed scheme. It is also shown that the reaction proceeds for an extended period of time in the dark following illumination, and a quantitative analysis is presented for this phase as well. The postulated model predicts that cerium(III) should have a cocatalytic or synergistic effect on the autoxidation of sulfite ion in the presence of other catalysts. This prediction was confirmed in the iron(III)-sulfite ion-oxygen system. The experimental method and the mathematical treatment used might be applicable to a wide range of photoinduced chain reactions.

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PubMed2004

Effect of dissolved oxygen on the oxidation of dithionate ion. Extremely unusual kinetic traces.

The effect of dissolved oxygen on the acid-dependent disproportionation of dithionate ion (S(2)O(6)(2-)) and its oxidation with a number of reagents (I(2), Br(2), I(3)(-), Br(3)(-), IO(3)(-), BrO(3)(-), IO(4)(-), MnO(4)(-), Cr(VI), Ce(VI), and H(2)O(2)) were studied. Dithionate ion is remarkably inert at room temperature, and heating to elevated temperatures (50-90 degrees C) was necessary to observe detectable reaction rates in all of these processes. It was confirmed that dithionate ion is never oxidized directly; its redox reactions are zeroth-order with respect to the oxidizing agent and proceed through disproportionation and subsequent fast oxidation of the sulfur(IV) formed. The effect of dissolved oxygen is attributable to its reaction with sulfur(IV) produced in the disproportionation. This autoxidation occurs only with a catalyst. Cerium(III) and iodide ions were shown to catalyze the autoxidation, and their effect on the kinetic traces was studied. In a few cases, highly unusual kinetic traces, such as straight lines with sharp break points, inverted parabolas, and a combination of these, were detected and successfully interpreted in terms of simple kinetic and stoichiometric considerations.

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PubMed2003

Complex formation reaction of the iron(III) hydroxo dimer with periodate ion.

The kinetics and mechanism of the ligand substitution reaction between Fe(2)(OH)(2)(4+) and periodate ion has been studied. This process is unique among the reactions of the iron(iii) hydroxo dimer because the initial rate is second-order with respect to Fe(2)(OH)(2)(4+). The formation of a bi- and a tetranuclear complex, Fe(2)(OH)(2)(H(4)IO(6))(3+) and Fe(4)(OH)(4)(H(4)IO(6))(7+), is proposed. Comprehensive fitting of the kinetic data was used to show that the proposed model, which is very similar to earlier models used with other inorganic oxoanions, gives a reasonable interpretation of all observations. It is shown that the lifetime of Fe(2)(OH)(2)(H(4)IO(6))(3+) is relatively long and it can open a pathway to form oligomeric and less soluble products at higher initial concentrations. The speciation of aqueous periodate ion solution was also studied and it is proposed that the tetrahedral form, IO(4)(-), is less dominant over the octahedral form, H(4)IO(6)(-), than previously thought.

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PubMed2003

Photoaccelerated oxidation of chlorinated phenols.

Exposure to visible light increases the rate of oxidation of chlorinated phenols by hydrogen peroxide in aqueous solution in either the presence or the absence of iron-based catalysts, which may be explained by the aqueous photoreactions of chloroquinone intermediates.

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PubMed2002

Synthesis and characterization of dimetallic oxorhenium(V) and dioxorhenium(VII) compounds, and a study of stoichiometric and catalytic reactions.

Chelating dithiolate ligands--e.g., mtp from 2-(mercaptomethyl)thiophenol, edt from 1,2-ethanedithiol, and pdt from 1,3-propanedithiol--stabilize high-valent oxorhenium(V) against hydrolytic and oxidative decomposition. In addition to the dithiolate chelating to a single rhenium, one sulfur forms a coordinate bond to the other rhenium. In one arrangement this gives a dimer with a nearly planar diamond core with different internal Re-S distances. The new compounds are [MeReO(edt)](2) (2) and [MeReO(pdt)](2) (3), which can be compared to the previously known [MeReO(mtp)](2) (1). Another mode of synthesis leads to [ReO](2)(mtp)(3) (5) and [ReO](2)(edt)(3) (6). They, too, have similar Re(2)S(2) cores that involve donor atoms from two of the dithiolate ligands; the third dithiolate chelates one of the rhenium atoms. Gentle hydrolysis of 1 affords [Bu(n)4][[MeReO(mtp)](2)(mu-OH)] (7) in low yield. It appears to be the first example of this structural type for rhenium. The use of dithioerythritol as a starting material allowed the synthesis of a dioxorhenium(VII) compound, [MeReO(2)](2)(dte) (8). Its importance lies in understanding the role such compounds are believed to play as intermediates in oxygen atom catalysis. Ligation of the dimers 1-3 converts them into monomeric compounds, MeReO(dithiolate)L. These reactions go essentially to completion for L = PPh(3), but reach an equilibrium for L = NC(5)H(4)R. With R = 4-Ph, the values of K/10(3) L mol(-1) for the reactions (1-3) + 2L = 2MeReO(dithiolate)L are identical within 3 sigma: 1.15(3) (1), 1.24(4) (2), and 1.03(16) (3). The rates of monomer formation follow the rate law -d ln [dimer]/dt = k(a)[L] + k(b)[L](2). These trends were found: (1) phosphines are slow to react compared to pyridines, (2) the edt dimer 2 reacts much more rapidly than 1 and 3. Dimer 1 and MeReO(mtp)PPh(3) both catalyze oxygen atom transfer: PicO + PPh(3) --> Pic + Ph(3)PO. Compound 1 is ca. 90 times more reactive, which can be attributed to its lability toward small ligands as opposed to the low rate of displacement of PPh(3) from the mononuclear catalyst. The kinetics of this reaction follows the rate law -d[PicO]/dt = k[PicO][1]/[1 + kappa[PPh(3)]], with k = 5.8 x 10(6) L mol(-1) s(-1) and kappa = 3.5 x 10(2) L mol(-1) at 23 degrees C in benzene. A mechanism has been proposed to account for these findings.

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PubMed2002

Ligand substitution kinetics of the iron(III) hydroxo dimer with simple inorganic ligands.

The kinetics and mechanisms of ligand substitution reactions of the iron(III) hydroxo dimer, Fe(2)(mu-OH)(2)(H(2)O)(8)(4+), with various inorganic ligands were studied by the stopped-flow method at 10.0 or 25.0 C in 1.0 M NaClO(4). The transient formation of the following di- and tetranuclear complexes was confirmed: Fe(2)(OH)SO(4)(3+), Fe(2)(OH)H(2)PO(2)(4+), Fe(2)(OH)HPO(3)(3+), Fe(2)(OH)SeO(3)(3+), and Fe(4)(AsO(4))(OH)(2)(7+). The catalytic effect of arsenic(III) on the hydrolytic reaction of iron(III) was also attributed to the formation of a dinuclear complex at very low concentration levels. Fast formation and subsequent dissociation of the multinuclear species into the corresponding mononuclear complexes (FeL) proceed via parallel reaction paths which, in general, show composite pH dependencies. The appropriate rate laws were established. The reactions of the different ligands occur at very similar rates, though the uninegatively charged singly deprotonated form reacts about 1 order of magnitude faster than the neutral form of the same ligand. The results can conveniently be interpreted in terms of a dissociative interchange mechanism which postulates the formation of an intermediate complex in which the ligand is coordinated to only one Fe(III) center of the hydroxo dimer. In a subsequent fast step, the ligand forms a bridge between the two metal ions by replacing one of the OH groups. The dissociation of the dinuclear complex into FeL most likely proceeds via the same intermediate.

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PubMed2002

Oxorhenium(V) dithiolates catalyze the oxidation by tert-butyl hydroperoxide of sulfoxides and sulfides, including 4,6-dimethyldibenzothiophene.

tert-Butyl hydroperoxide (TBHP) efficiently converts a wide variety of sulfides to sulfoxides and sulfones. The method offers the advantage that one product or the other can be obtained in high purity by a modest variation of conditions. The reactions occur smoothly at 25minus sign50 C in chloroform and, to the extent studied, in toluene and methylene chloride. A catalyst is required; the most extensively studied was MeReO(mtp)PPh(3), 1, where mtpH(2) is 2-(mercaptomethyl)thiophenol. Other chelating dithiolate ligands can be used with comparable results. These oxidations were tested for dialkyl, alkylminus signaryl, and diaryl sulfides; thiophenes; and thianthrene. Even the "hard" sulfide, 4,6-dimethyldibenzothiophene (DMDBT) was quantitatively oxidized to the dioxide with TBHP:DMDBT 3.0-3.5 and 0.05-3.8 mol % 1. The mechanism was explored in kinetics studies carried out only for methyl tolyl sulfide. The product buildup curve was complex, with an induction period followed by a rapid growth phase. The kinetic data could be modeled adequately but not perfectly by allowing five rate constants to refine. Their values are consistent with the chemical sense of the mechanism.

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PubMed1998

The Early Phase of the Iron(III)-Sulfite Ion Reaction. Formation of a Novel Iron(III)-Sulfito Complex.

The kinetics and mechanism of the iron(III)-sulfite ion reaction were studied by using the stopped-flow method at 10.0 degrees C in 1.0 M NaClO(4). The formation of a 1:1 and a 2:1 complex was confirmed in the initial phase of the reaction when the metal ion was in excess over the ligand. In this system the formation of the dimer complex, Fe(2)S(IV), was not reported before. The following composition is proposed for the new species: (H(2)O)(4)Fe(SO(3))(OH)Fe(H(2)O)(4)(3+). The stability constant of the complex formation reaction, Fe(2)(OH)(2)(4+) + HSO(3)(-) right harpoon over left harpoon Fe(2)S(IV), was determined from absorbance data at 430 nm: log K(21) = 3.37 +/- 0.16. According to detailed kinetic studies the complex formation is first order in both Fe(2)(OH)(2)(4+) and sulfite ion. The pH dependence of the measured rate constants indicates two kinetically significant pathways with the SO(3)(2-) and HSO(3)(-) forms of the ligand, respectively. The corresponding rate constants are the following: k(HSO)()3()- = (4.5 +/- 0.3) x 10(4) M(-1) s(-1) and k(SO)()3()2- = (2.1 +/- 0.2) x 10(9) M(-1) s(-1). Mechanistic aspects of the complex formation are discussed in detail.

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