Reactions of Mixed-Valent Palladium (IV,II) Complexes of Tetradentate Schiff-Bases Involving Bond Isomerization

Reactions of [PdIVB-(AI)2]++ [PdIICl4]-- (i) B-(AI)2 = dianion of N,N'-ethylene-/i-propylene-/n-propylene-bis(acetyl-acetoneimine) with some π-acceptor ligands, aliphatic primary amines and nitrosating reagents have been investigated. In all these reactions except nitrosation, 1:1 adducts having the formula, [PdIVB-(AI)2.X] [PdIICl4] [X = triphenylphosphine (TPP), triphenylarsine (TPA), pyridine (Py), methylamine (CH3NH2) or ethylamine (C2H5NH2)] are obtained. The formation of these complexes is associated with a bond isomerization - from Pd-Cxo-π -allylic bond prevailing in [PdIVB-(AI)2]2+ to PdIV-O bonding.Reaction of (i) with nitrosating reagents reduces PdIV to PdII and subsequently transform the γ-CH group, into an ambidentate isonitroso group (°C = NOH). The latter enters into coordination with PdII by dislodging the already coordinated carbonyl group. Further, selective nitrosation (mono- and dinitrosation) has been carried out by controlling the amount of the nitrosating reagent and the reaction time. The complexes have been characterized by elemental analyses, electrical conductivity, magnetic susceptibility and ir spectral data.

Lewis Acid-Lewis Base Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation

Organocatalysis, the use of organic molecules as catalysts, is attracting increasing attention as one of the most modern and rapidly growing areas of organic chemistry, with countless research groups in both academia and the pharmaceutical industry around the world working on this subject. The literature review of this thesis mainly focuses on metal-free systems for hydrogen activation and organocatalytic reduction. Since these research topics are relatively new, the literature review also highlights the basic principles of the use of Lewis acid-Lewis base pairs, which do not react irreversibly with each other, as a trap for small molecules. The experimental section progresses from the first observation of the facile heterolytical cleavage of hydrogen gas by amines and B(C6F5)3 to highly active non-metal catalysts for both enantioselective and racemic hydrogenation of unsaturated nitrogen-containing compounds. Moreover, detailed studies of structure-reactivity relationships of these systems by X-ray, neutron diffraction, NMR methods and quantum chemical calculations were performed to gain further insight into the mechanism of hydrogen activation and hydrogenation by boron-nitrogen compounds.

Catalytic hydrogen combustion for treatment of combustible gases from fuel cell processors

Catalytic combustion of H-2 was carried out over combustion synthesized noble metal (Pd or Pt) ion-substituted CeO2 based catalysts using a feed stream that simulated exhaust gases from a fuel cell processor The catalysts showed a high activity for H-2-combustion and complete conversion was achieved below 200 C over all the catalysts when O-2 was used in a stoichiometric amount With higher amounts of O-2 the reaction rates Increased and complete conversions were possible below 100 C The reaction was also carried out over Pd-impregnated CeO2 The conversions of H-2 with stoichiometric amount of O-2 were found to be higher over Pd-substituted compound The mechanism of the reaction over noble metal-substituted compounds was proposed on the basis of X-ray photoelectron spectroscopy studies The redox couples between Ce and metal ions were established and a dual site redox mechanism was pi posed for the reaction (C) 2010 Elsevier B V All rights reserved

Functional Mimics of Glutathione Peroxidase: Bioinspired Synthetic Antioxidants

Oxidative stress is caused by an imbalance between the production of reactive oxygen species (ROS) and the biological system's ability to detoxify these reactive intermediates. Mammalian cells have elaborate antioxidant defense mechanisms to control the damaging effects of ROS. Glutathione peroxidase (GPx), a selenoenzyme, plays a key role in protecting the organism from oxidative damage by catalyzing the reduction of harmful hydroperoxides with thiol a ``catalytic triad'' with tryptophan and glutamine, which cofactors. The selenocysteine residue at the active site forms activates the selenium moiety for an efficient reduction of peroxides. After the discovery that ebselen, a synthetic organoselenium compound, mimics the catalytic activity of GPx both in vitro and in vivo, several research groups developed a number of small-molecule selenium compounds as functional mimics of GPx, either by modifying the basic structure of ebselen or by incorporating some structural features of the native enzyme. The synthetic mimics reported in the literature can be classified in three major categories: (i) cyclic selenenyl amides having a Se-N bond, (ii) diaryl diselenides, and (iii) aromatic or aliphatic monoselenides. Recent studies show that ebselen exhibits very poor GPx activity when aryl or benzylic thiols such as PhSH or BnSH are used as cosubstrates. Because the catalytic activity of each GPx mimic largely depends on the thiol cosubstrates used, the difference in the thiols causes the discrepancies observed in different studies. In this Account, we demonstrate the effect of amide and amine substituents on the GPx activity of various organoselenium compounds. The existence of strong Se ... O/N interactions in the selenenyl sulfide intermediates significantly reduces the GPx activity. These interactions facilitate an attack of thiol at selenium rather than at sulfur, leading to thiol exchange reactions that hamper the formation of catalytically active selenol. Therefore, any substituent capable of enhancing the nucleophilic attack of thiol at sulfur in the selenenyl sulfide state would enhance the antioxidant potency of organoselenium compounds. Interestingly, replacement of the sec-amide substituent by a tert-amide group leads to a weakening of Se ... 0 interactions in the selenenyl sulfide intermediates. This modification results in 10- to 20-fold enhancements in the catalytic activities. Another strategy involving the replacement of tert-amide moieties by tert-amino substituents further increases the activity by 3- to 4-fold. The most effective modification so far in benzylamine-based GPx mimics appears to be either the replacement of a tert-amino substituent by a sec-amino group or the introduction of an additional 6-methoxy group in the phenyl ring. These strategies can contribute to a remarkable enhancement in the GPx activity. In addition to enhancing catalytic activity, a change in the substituents near the selenium moiety alters the catalytic mechanisms. The mechanistic investigations of functional mimics are useful not only for understanding the complex chemistry at the active site of GPx but also for designing and synthesizing novel antioxidants and anti-inflammatory agents.

Curing reactions in plastic prepolymers and propellants. I. Polystyrene

Curing reactions of the viscous PS prepolymer and PS/AP propellant slurry have been studied. The molecular weight of the binder (separated from the propellant) and the prepolymer was found to increase to a maximum value, remain constant for some time, and then fall off between 50–125°C. The molecular weight of the binder was found to be less than corresponding prepolymer between 100–150°C but at lower temperatures (50–75°C) the reverse was found to be true. The increase in the molecular weight during curing at lower temperatures has been explained on the basis of Trommsdorff effect which gets support from the estimated activation energy (9 kcal mole−1) for the curing process. Curing was recognized as chain extension where the rate of polymerization becomes diffusion controlled below 75° C.

High-Surface Step Density on Dendritic Pd Leads to Exceptional Catalytic Activity for Formic Acid Oxidation

Dendrite Pd with corrugated surfaces, obtained by a novel AC technique, exhibits an exceptionally high catalytic activity for the oxidation of formic acid because of the presence of a high density of surface steps. The formation of twinned dendrites leads to a predominance of exposed 111 facets with a high density of surface steps as evident from high resolution electron microscopy investigations. These surface sites provide active sites for the absorption of the formic acid molecules, thereby enhancing the reaction rate. Control experiments by varying the time of deposition reveal the formation of partially grown dendrites at shorter times indicating that the dendrites were formed by growth rather than particle attachment. Our deposition method opens up interesting possibilities to produce artisotropic nanostructures with corrugated surfaces by exploiting the perturbations involved in the growth process.

Global, Local and Vector-Valued Tb Theorems on Non-Homogeneous Metric Spaces

Various Tb theorems play a key role in the modern harmonic analysis. They provide characterizations for the boundedness of Calderón-Zygmund type singular integral operators. The general philosophy is that to conclude the boundedness of an operator T on some function space, one needs only to test it on some suitable function b. The main object of this dissertation is to prove very general Tb theorems. The dissertation consists of four research articles and an introductory part. The framework is general with respect to the domain (a metric space), the measure (an upper doubling measure) and the range (a UMD Banach space). Moreover, the used testing conditions are weak. In the first article a (global) Tb theorem on non-homogeneous metric spaces is proved. One of the main technical components is the construction of a randomization procedure for the metric dyadic cubes. The difficulty lies in the fact that metric spaces do not, in general, have a translation group. Also, the measures considered are more general than in the existing literature. This generality is genuinely important for some applications, including the result of Volberg and Wick concerning the characterization of measures for which the analytic Besov-Sobolev space embeds continuously into the space of square integrable functions. In the second article a vector-valued extension of the main result of the first article is considered. This theorem is a new contribution to the vector-valued literature, since previously such general domains and measures were not allowed. The third article deals with local Tb theorems both in the homogeneous and non-homogeneous situations. A modified version of the general non-homogeneous proof technique of Nazarov, Treil and Volberg is extended to cover the case of upper doubling measures. This technique is also used in the homogeneous setting to prove local Tb theorems with weak testing conditions introduced by Auscher, Hofmann, Muscalu, Tao and Thiele. This gives a completely new and direct proof of such results utilizing the full force of non-homogeneous analysis. The final article has to do with sharp weighted theory for maximal truncations of Calderón-Zygmund operators. This includes a reduction to certain Sawyer-type testing conditions, which are in the spirit of Tb theorems and thus of the dissertation. The article extends the sharp bounds previously known only for untruncated operators, and also proves sharp weak type results, which are new even for untruncated operators. New techniques are introduced to overcome the difficulties introduced by the non-linearity of maximal truncations.

Dynamics of activationless reactions in solution

Recent picosecond and subpicosecond laser spectroscopy experiments have revealed several chemically and biologically important reactions in solution in which the reaction potential surface does not present a barrier to the motion along the reaction coordinate.The dynamics of these reactions display diverse and interesting behavior. They include the dependence of relaxation rate on the solvent viscosity, the solvent polarity, the temperature, and the wavelength of the exciting light. In this article we review the recent developments in the theoretical description of activationless processes in solution and compare them with the available experimental results

Noble metal ionic sites for catalytic hydrogen combustion: spectroscopic insights

A catalytic hydrogen combustion reaction was carried out over noble metal catalysts substituted in ZrO2 and TiO2 in ionic form. The catalysts were synthesized by the solution combustion technique. The compounds showed high activity and CO tolerance for the reaction. The activity of Pd and Pt ion substituted TiO2 was comparable and was higher than Pd and Pt ion substituted ZrO2. The mechanisms of the reaction over the two supports were proposed by making use of the X-ray photoelectron spectroscopy and FT infrared spectroscopic observations. The reaction over ZrO2 supported catalysts was proposed to take place by the utilization of the surface hydroxyl groups while the reaction over TiO2 supported catalysts was hypothesized to be a hybrid mechanism utilizing surface hydroxyl groups and the lattice oxygen.