Electrophilic Substitution Reactions of Copper(II) Acetylacetoneimine Complexes with Arene Diazonium Ions

Copper(II) complexes of ethylene/propylene-bis(acetylacetoneimine), Cu(baen) or Cu(bapn), react quickly and quantitatively in aqueous methanol at the methine position with arene diazonium ions in a stepwise manner to yield mono- and di-substituted copper(II) complexes. All the complexes are paramagnetic with μeff∼1.88 B.M. In all the complexes the diazo substituted part of the ligand coordinates to the metal through the agr-nitrogen of the azo group and the imine nitrogen, forming glyoxaliminearylhydrazone type of ligand system. The complexes have been characterized by elemental analysis, electronic, esr, ir and mass spectroscopic methods.

Structure and thermal stability relationships in ring-substituted arylammonium nitrates

The thermal stability of ring-substituted arylammonium nitrates has been investigated using thermal methods of analysis. The decomposition temperature of meta- and para-substituted derivatives is found to be linearly related to the Hammett substituent constant σ. The activation energy for decomposition determined by isothermal gravimetry increases with the increasing basicity of the corresponding amine. The results suggest that the primary step in the decomposition process of these salts is proton abstraction by the anion from the arylammonium ion.

Structure and explosive sensitivity relation in ring-substituted arylammonium perchlorates

The thermal and explosive characteristics of ring-substituted arylammonium perchlorates have been studied by differential thermal analysis, explosion delay, and impact-sensitivity measurements. The decomposition and dissociation temperatures, as well as activiation energy for explosion, increase with increasing basicity of the corresponding arylamine. These parameters, when plotted against σ, the Hammett substituent constant, show a linear relationship in the case of meta- and para-substituted derivatives. The results indicate that a proton transfer from arylammonium ion to perchlorate ion is involved in the decompostion and also in the explosion process of these arylammonium perchlorates.

Novel coordination behaviour of gem-bis (pyrazolyl) cyclotriphosphazenes as tridentate NNN-donor ligands: The crystal structure of [Mo(CO)3{N3P3Ph4(3,5-Me2C3HN2)2}]

Reactions of group 6 metal carbonyls with bis(pyrazolyl) phosphazenes yield metal tricarbonyl complexes, [M(CO)3.L] [L = N3P3Ph4 (3, 5-Me2C3HN2)2 (1) or N3P3(MeNCH2CH2O)2 (3,5-Me2C3HN2)2(4)]. The structure of the complex [Mo(CO)3.1], determined by single-crystal X-ray analysis, shows that the (pyrazolyl) phosphazene acts as a tridentate ligand; the two pyridinic pyrazolyl nitrogen atoms and a phosphazene ring nitrogen atom are coordinated to the metal. A similar structure is proposed for the complexes [M(CO)3.4] (M = Mo or W] on the basis of their spectroscopic data.

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.

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.

Studies on ß-arylhydrazone-imine nickel(II) complexes—Examples of metal template syntheses

ß-arylhydrazone-imine ligand complexes of nickel(II), namely, 4,10-dimethyl-5,9-diazatrideca-4,9-diene-2,12-dione-3,11-diphenylhydrazonato nickel(II), Ni(acacpn)(N2Ph-R)2 and 1,11-diphenyl-3,9-dimethyl-4,8-diazaun-deca-3,8-diene,1,11-dione-2,10-diphenyl hydrazonato nickel(II), Ni (beacpn) (N2Ph-R)2, [R = H, o-CH3p-CH3] have been prepared by metal template reactions and characterized. Both the azomethine nitrogens and α-nitrogens of bis-hydrazone form the coordination sites of the square-planar geometry around the nickel(II) ion. Loss of CO from the molecule and subsequently an interesting methyl group migration to the nucleus of the chelate ring have been observed in the mass spectrum. Structures are proposed based on the spectral and magnetic properties.