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SynopsisReactivity trends of thioethers toward square-planar complexes can be generally interpreted by use of an equation of the form: log k = γ + α∑σ* + βθ, where k denotes second-order rate constants, ∑σ* the sum of Taft constants for the thioether substituents, and θ the thioether cone angles. γ represents an intrinsic parameter for each substrate complex, while α is an electronic and β a steriSynopsisReactivity trends of thioethers toward square-planar complexes can be generally interpreted by use of an equation of the form: log k = γ + α∑σ* + βθ, where k denotes second-order rate constants, ∑σ* the sum of Taft constants for the thioether substituents, and θ the thioether cone angles. γ represents an intrinsic parameter for each substrate complex, while α is an electronic and β a steri

SynopsisOptimized structures describing key features of the potential energy surface for water exchange at three planar d8 centers have been calculated using ab initio density functional theory. The local density approximation (LDA), including relativistic corrections for Pt, gives good agreement with the available experimental ground state structural data. LDA binding energies together with expli

SynopsisVarious protolytic species of thiols RSH (thioglycolic acid, l-cysteine, dl-penicillamine, and glutathione) in rapid equilibria with each other reduce trans-[Pt(CN)4Cl2]2- in parallel, halide-bridged electron transfer reactions. A linear Brønsted correlation between the reactivity of the thiolate anions RS- and their basicity is observed. The mechanism derived might be used as a model for

SynopsisReduction of gold(III) complexes by thiocyanate takes place via rapid substitutions at gold(III), followed by intramolecular, slower reductive elimination through attack by outer-sphere thiocyanate. A transition state with an S−S interaction between attacking and coordinated thiocyanate is suggested for the redox process.AbstractAbstract ImageKinetics for reactions between thiocyanate and SynopsisReduction of gold(III) complexes by thiocyanate takes place via rapid substitutions at gold(III), followed by intramolecular, slower reductive elimination through attack by outer-sphere thiocyanate. A transition state with an S−S interaction between attacking and coordinated thiocyanate is suggested for the redox process.AbstractAbstract ImageKinetics for reactions between thiocyanate and

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SynopsisReversible formation and proton-assisted aquation of 1:1 monodentate carboxylate complexes of palladium(II) takes place via a transition state stabilized by hydrogen bonding in an activation process strongly dominated by bond making. Volume profiles have been established through high-pressure kinetic measurements.AbstractAbstract ImageKinetics and equilibria for reversible formation of 1:1SynopsisReversible formation and proton-assisted aquation of 1:1 monodentate carboxylate complexes of palladium(II) takes place via a transition state stabilized by hydrogen bonding in an activation process strongly dominated by bond making. Volume profiles have been established through high-pressure kinetic measurements.AbstractKinetics and equilibria for reversible formation of 1:1 monodentate c

Autoxidation of SO2(aq) in the presence of manganese(II) is one of the important pathways for sulfuric acid formation in atmospheric clouds and fogs. Recent experimental results indicating that the catalyzed reaction takes place via a complex free-radical mechanism are discussed. Previous literature is reviewed in the light of this mechanism. Under atmospheric conditions of low total concentrationAutoxidation of SO2(aq) in the presence of manganese(II) is one of the important pathways for sulfuric acid formation in atmospheric clouds and fogs. Recent experimental results indicating that the catalyzed reaction takes place via a complex free-radical mechanism are discussed. Previous literature is reviewed in the light of this mechanism. Under atmospheric conditions of low total concentration

Reduction of [AuCl4]- and trans-[Au(CN)2X2]- (X = Cl, Br) by sulfur(IV) as SO2.nH2O, HSO3-, and SO3(2-) has been studied at 25-degrees-C in aqueous solution with ionic strength 1.0 M and 0 < pH < 2.3 by use of stopped-flow spectrophotometry. Redox takes place directly without initial substitution at the gold(III) centers with stoichiometry Au(III):S(IV) = 1:1 and with Au(I) complexes and HSO4- as

This paper reports the results of a production experiment that explores the prosodic realization of focus in Hungarian, a language that is characterized by obligatory syntactic focus marking. Our study investigates narrow focus in sentences in which focus is unambiguously marked by syntactic means, comparing it to broad focus sentences. Potential independent effects of the salience (textual givenn

The Swedish National Innovation Council (NIC) was created by the Prime Minister (Stefan Löfven) in February 2015, and it has now been operating for 18 months. It is personally chaired by the Prime Minister, which is unusual for such councils in other countries. Another atypical characteristic of the Swedish NIC is its dominant and wide focus on innovation rather than on research (for which there i

Heavy combined lung weight at autopsy is a non-specific autopsy finding associated with certain causes of death such as intoxication. There is however no clear definition of what constitutes "heavy" lung weight. Different reference values have been suggested but previous studies have been limited by small select populations and only univariate regression has been attempted. The aim of this study w

Purpose: Radiation therapy with protons, owing to its physical properties, can beadvantageous for the treatment of children. This study was conducted in order to quantify the advantages of proton therapy from a treatment planning point of view in a consecutive, realistic, and mixed pediatric/adolescent population with varying diagnoses and target locations.Patients and Methods: Forty-five patients