Darstellung und spektroskopische Eigenschaften von Nitridophthalocyaninatorhenium(V)

Preparation and Spectroscopical Properties of Nitridophthalocyaninatorhenium(V) Nitridophthalocyaninatorhenium(V) ([ReNPc^2?]) is prepared by the reaction of dirheniumheptoxide with ammoniumiodide in molten 1,2-dicyano-benzene. The diamagnetic complex is chemically und thermically extremely stable. In the Uv-vis spectra the typical π-π*-transitions of the Pc^2? ligand are observed. Extra bands in the solid state spectrum are due to strong excitonic coupling of ca. 2.8 kK. In the resonance Raman spectra the intensity of the Re≡N stretching vibration (v(Re≡N)) at 969 cm^?1 is selectively enhanced by laser excitations above 19.0 kK. v(Re≡N) is a dominant m.i.r. absorption at 976 cm^?1.     

Osmium(II)-Phthalocyanine: Darstellung und Eigenschaften von Di(acido)phthalocyaninatoosmaten(II)

Osmium(II) Phthalocyanines: Preparation and Properties of Di(acido)phthalocyaninatoosmates(II) “H[Os(X)₂Pc^2?]” (X = Br, Cl) reacts in basic medium or in the melt with (ⁿBu₄N)X forming less stable, diamagnetic, darkgreen (ⁿBu₄N)₂[Os(X)₂Pc^2?]. Similar dicyano and diimidazolido(Im) complexes are formed by the reaction of “H[Os(Cl)₂Pc^2?]” with excess ligand in the presence of [BH₄]^?. The cyclic voltammograms show up to three quasireversible redoxprocesses: E_1/2(I) = 0.13 V (X = CN), ?0.03 V (Im), ?0.13 V (Br) resp. ?0.18 V (Cl) is metal directed (Os^II/III), E_1/2(II) = 0.69 V (Cl), 0.71 V (Br), 0.83 V (CN), 1.02 V (Im) is ligand directed (Pc^2?/?) and E_1/2(III) = 1.17 V (Cl) resp. 1.23 V (Br) is again metal directed (Os^III/IV). Between the typical “B” (～16.2 kK) and “Q” (～29.4 kK), “N regions” (～34.1 kK) up to seven strong “extra bands” of the phthalocyanine dianion (Pc^2?) are observed in the uv-vis spectrum. Within the row CN > Im > Br > Cl, most of the bands are shifted slightly, the “extra bands” considerably more to lower energy in correlation with E_1/2(I). The vibrational spectra are typical for the Pc^2? ligand with D_4h symmetry. M.i.r. bands at 514, 909, 1 173 and 1 331 cm^?1 are specific for hexa-coordinated low spin Os^II phthalocyanines. In the resonance Raman (r.r.) spectra polarized, depolarized or anomalously polarized deformation and stretching vibrations of the Pc^2? ligand will be selectively enhanced, if the excitation frequency coincides with “extra bands”. With excitation at ～19.5 kK the intensity of the symmetrical Os? X stretching vibration at 295 cm^?1 (X = Cl), 252 cm^?1 (X = Im) and 181 cm^?1 (X = Br) is r.r. enhanced, too. The asymmetrical Os? X stretching vibration is observed in the f.i.r. spectrum at 345 cm^?1 (X = CN), 274 cm^?1 (X = Cl), 261 cm^?1 (X = Im) and 200 cm^?1 (X = Br).     

ChemInform Abstract: Photoionization Spectra of Cesium and Cesium Oxide Clusters.

Seven cesium and 86 oxidized cesium clusters, CsnOm (0 < m < n; n = 3-14), are ionized in a one-photon process by means of a tunable cw dye laser and detected in a mass spectrometer.     

ChemInform Abstract: The Characterization of Molecular Boric Acid by Mass Spectrometry and Matrix Isolation IR Spectroscopy.

Molecular H₃BO₃ is obtained by heating crystalline orthoboric acid in vacuo to ∼ 40 °C. The IR spectrum of this species isolated in low-temp.     

ChemInform Abstract: Photochemistry of Aqueous Tetrathioantimonate(V).

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

ChemInform Abstract: Quantum Molecular Interpretation of Photodetachment and Photodepletion Spectra of Small Alkali Metal Clusters.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

ChemInform Abstract: Dimers and Tetramers of SiCl in a Molecular Beam from a Heterogeneous,Intermediate-Pressure Reactor.

Unusual molecules like Si₂Cl₂ and Si₄Cl₄ can be detected by mass spectrometry in a molecular beam extracted from a promising new type of source.     

ChemInform Abstract: Experimental Evidence for the Existence of Neutral P6: A New Allotrope of Phosphorus.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.