The number and relative energies of nitrate combination frequencies in the 1700–1800 cm−1 region of the infrared spectrum may be used as an aid to distinguish the various coordination modes of the nitrate group. The data also provide an excellent probe for the strength of the metal–nitrate interaction.

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Tetrahedral and octahedral cobalt(II), and square and octahedral nickel(I1) complexes of 1,2-bis(2'-imidazolin-2'-yl)benzene, 1,2-bis(2'-imidazolin-2'-yl)ethane, and some imidazoline ring methyl substituted ligands are reported. The structures are confirmed by three X-ray structural analyses, magnetism, and electronic and vibrational (conventional and far i.r.) spectroscopy. Both cis and trans octahedral complexes of the type M(ligand)z(NCS)z [M = Co(II), Ni(II)] have been characterized, and none of these exhibit splitting of the v(CN)(NCS) absorption in the i.r. spectrum at room temperature. Low temperature studies reveal splitting of the v(CN) band in the cis isomers. Both 13C and I5N satellite absorption is identified. The delocalization of the double bond in the imidazoline rings in these complexes is discussed in terms of the i.r. and X-ray data.Canadian Journal of Chemistry, 48, 3076 (1970) We report here the metal complexing ability calibrant. The U.V. spectra were recorded with a Cary 14 of some novel bidentate ligands containing spectrometer and molecular weight data with a modified Gallenkamp Model 7665K semi-micro ebulliometer, imidazoline rings.the coordination calibrated with azobenzene and with benzoic acid. Infrachemistry of imidazole and its derivatives has red and far i.r. data were obtained with a Beckman IR 12 been extensively investigated (1, 2), studies of its spectrometer, and magnetic susceptibilities, via the Gouy dihydro derivative are restricted to the chemistry method with an Alpha 4 in. magnet calibrated with of 2,2,-bi-2-imidazoline (3). since the dihydro mercury cobalt tetrathiocyanate. Low temperature electronic and vibrational data were obtained with a Beckman ligand is somewhat simpler than imidazole, being V L T -~ Variable Temperature Cell, with quartz (elecnon-aromatic, it was thought that a study of its tronic), o r NaCl (i.r.) windows. Microanalyses were metal complexing ability might prove rewarding. substituted derivative (4, LME) were synthesized TO 1,3-diiminoisoindoline (6) (7.25 g, 0.05 mole) disby the phosphorus pentasulfide catalyzed reaction solved in boiling absolute ethanol, was added ethyleneof ethylenediamine (or 1,2-propanediamine) with diamine (6.2 g, 0.1 mole) and the mixture refluxed until phthalodinitrile or succinonitrile, a standard evolution of ammonia had ceased. The bulk of the solvent was removed by distillation at reduced pressure until route for the preparation Of imidazolines (4). crystallization occurred. The white crystalline product The ethane derivative LE has been reported (5) (6.1 g, 60% yield) was recrystallized from benzene. T h e but the other ligands were previously unknown. pure product melted at 174-175". Reaction of the parent ligands with cobalt and Method B (Based on (7)) nickel salts in alcohol led to the isolation of a 0-Dicyan~benzene (6.4 g, 0.05 mole), ethylenediamine series of square, tetrahedral, and octahedral (6.2 g, 0.1 mole), and a catalytic amount of phosphorus pentasulfide (20 mg) were mixed together. Upon applicacomp...

The mapping of the energy levels in metallophthalocyanines is accomplished by a combination of electrochemistry, electronic spectroscopy, and photochemistry. This chapter reviews the electrochemical properties of metallophthalocyanines and includes a large amount of previously unpublished data. The results are rationalized in terms of the nature of the electron transfer, that is, redox at metal or ligand. Well--defined correlations are shown to exist between the ease of oxidation or reduction of the phthalocyanine ligand and the oxidation state, and/or polarizing power, of the metal ion. Solvent and ring substitution effects also are presented and explained. Charge transfer transition energies can be calculated directly from these data, and agreement between experiment and theory is excellent. Finally, the data are used to calculate both the photo--generated excited state redox energies and the thermodynamics of quenching by donors and acceptors.TOhthalocyanine (MPc) complexes have significant importance for many reasons, including their similarity to the biologically impor tant metalloporphyrins, their classical use as dyestuffs, and their de veloping use as components of various solar energy conversion de vices.