Molecular electronic structure of metal phthalocyanines

The molecular–electronic structure of the metal phthalocyanines (Fe, Co, Ni and Cu) has been determined by the molecular orbital treatment. Coulomb integrals of the metal atom occurring in the secular determinants have been approximated equivalent to the valence state ionization energy (VSIE) of a metal orbital for a particular charge configuration. The calculated π-electron charge densities have been found to be higher on the nitrogen atoms as compared to the other atoms in the molecule. This is in agreement with the e.s.r. studies of the metal phthalocyanines. To test the correctness of the molecular orbital calculations, the π-π* transitions (14,000 cm^?1 ? 30000 cm^?1), d-d* transitions (20000 cm^?1 ? 60000 cm^?1) and charge transfer transitions (15000 cm ^?1 ? 30000 cm^?1) have been calculated in the metal phthalocyanine molecules. The calculated frequencies have been compared with the observed ones and found in fair agreement.     

Oxidations by iron(VI). Kinetic study of uncatalysed and osmium(VIII) catalysed oxidation of dimethyl sulphoxide in alkaline medium

Summary Uncatalysed and Os^VIII-catalysed oxidation of dimethyl sulphoxide (DMSO) by potassium ferrate [Fe^VI] has been studied in alkaline medium in the 9.8–11.9 pH range, in the presence of IO ₄ ^– as a stabilizing agent. The order in [Fe^VI] and [DMSO] was found to be unity for the uncatalysed reaction and zero and fractional respectively for the catalysed reaction. The [Os^VIII] order was unity in the catalysed reaction. The rate of oxidation decreased with increase in pH and the order in [H⁺] was fractional for the uncatalysed oxidation. However in the catalysed oxidation, the rate at first decreased and then increased with increase in pH. The effect of changing [IO ₄ ^– ] and [buffer] on the oxidation rate was negligible in both cases. Suitable mechanisms consistent with the observed kinetics have been proposed.     

Convenient Procedure for Dethioketalisation in Nitrogen Heterocycles

Regeneration of Carbonyl compounds from the corresponding thioketals in nitrogen heterocycles have been effected using Dowex 50W acidic catalyst in reasonable yields.     

Diorganotin(IV) complexes derived from thiazole Schiff bases: synthesis,characterization, antimicrobial and cytotoxic studies

Research on Chemical Intermediates - Organotin(IV) complexes are gaining major attention as drug candidates, accordingly we have synthesized a cluster of novel diorganotin(IV) complexes R2SnClL...     

Thermal, magnetic and spectral properties of metal quinone complexes

The reactions of 3-chloro-2-hydroxy-1,4-naphthoquinone; chlorolawsone with “Na” metal (ClLw-1), CH₃COONa (ClLw-2), NaOH (ClLw-3), KOH (ClLw-4) and K₂CO₃ (ClLw-5) have been studied. Dark brown solids obtained for ClLw-1 to ClLw-5 are characterized by elemental analysis FTIR, ¹HNMR, UV–Visible spectroscopy, thermogravimetric analysis and DSC studies. FTIR of ClLw-1 to ClLw-5 shows decrease in ν_C=O frequency after complexation of alkali metal ions and ν_OH of adsorbed as well as coordinated water molecules have been observed between 3,600 and 3,100 cm^?1. The benzenoid protons C(5)H and C(8)H shows down field shift due to intermolecular hydrogen bonding interaction with neighboring molecules and upfield shift have been observed for C(6)H and C(7)H protons in ClLw-1 to ClLw-5 in ¹HNMR spectra. Bathochromic shift ~2 to ~5 nm have been observed for band at 287 nm. The nature of pyrolytic decomposition in chlorolawsone anion in ClLw-1 to ClLw-5 has been observed to be “gradual-1–abrupt–gradual-2”. Phase transition occurred during gradual-1 pyrolytic decomposition of chlorolawsone anion in ClLw-1 to ClLw-4 has been studied by DSC.     

Development of high ionic-conductive Li1.5Al0.5Ge1.5(PO4)3 glass-ceramic solid electrolyte sheet at low temperature using glass/powder composite

Journal of Solid State Electrochemistry - Because of some drawbacks of the organic electrolytes, such as high toxicity and flammability, inorganic electrolytes have attracted attention regarding...     

Attempts directed towards the synthesis and determination of the absolute stereochemistry of iso-cladospolide-B and cladospolides-B and C

Attempts to synthesise iso-cladospolide-B, cladospolide-B and cladospolide-C resulted in macrolides 1, 2 and 4 along with butenolide 3. Of the three stereogenic centres, the C-4/C-5 vic-diol was obtained from tartaric acid and d-glucose, while the C-11 stereocentre was created by Jacobsen’s method.     

Design, synthesis, and structural aspects of chalcogen-substituted pyridine dicarboxamide donors and their reactions

The design and synthesis of a new family of potentially pentadentate N₃Se₂ or N₃Te₂ type donors bearing a 2,6-disubstituted pyridine dicarboxamide moiety as the central fragment [-NH-C(O)-pyridine-C(O)-NH-] functionalized with chalcogen as additional donors in the appended arms of the pyridine ring through the alkyl spacers and their potential applications and reactivity toward d⁸ and d¹⁰ metal ions have been demonstrated.