Infrared spectra of metal β-ketoenolates and related complexes

A. Scope of the review 173 B. The assignment problem 174 C. Metal fi-ketoenolates 187 D. Metal /I-ketoenolates 192 E. Ligand substitution in metal /I-ketoenolates 195 F. Adducts of transition metal B-ketoenolates 208 G. Uranyl and vanadyl /I-ketoenolates 227 H. Derivatives of metal acetylacetonates in which one or both 0 atoms have been substituted by NH, S or Se 239 Acknowledgements 246 References 246

Infrared spectra of metal p-ketoenolates and related complexes

Neutral organophosphorus chalcogenide-metal salt interactions: Addition and decomposition products

Transformation of square-planar dsp2 configuration of Ni(II) aldoximates into octahedral sp3d2 configuration by reaction with tin(IV) chloride

Infrarot- und Raman-Festkorperspektren folgender Verbindungen werden mitgeteilt: Cl3B · OPCl3, Cl3B · OPBr3, Br3B · OPCl3, Br3B · OPBr3, Cl3Al · 2 OPCl3, ferner die IR-Spektren der Verbindungen Cl3Al · OPCl3, Br3Al · OPCl3, Cl3Al · OPBr3, Br3Al · OPBr3, Cl3Ga · OPCl3, Cl3In · OPCl3, Cl3Tl · 2 OPCl3. Die beobachteten Banden der Valenzschwingungen werden zugeordnet. In allen Fallen wird gefolgert, das die Anlagerung uber den Sauerstoff des Phosphoroxidhalogenids erfolgt, da eine starke Erniedrigung der PO-Valenzfrequenz zu erkennen ist. Die Kreftkonstanten kPO und kBo werden nach einem einfachen Ansatz berechnet. Mit steigendem Atomgewicht nimmt die Wechselwirkung zwischen dem Halogenid und Phosphoroxidchlorid ab. Die Darstellng der Verbindung Cl3B · SPCl3 gelang nicht.



The vibratinal spectra in the solid state of the addition compounds Cl3B · OPCl3, Cl3B · PBOr3, Br3B · OPCl3, Br3B · OPBr3, Cl3Al · 2 OPCl3, Cl3Al · OPCl3, Br3Al · OPCl3, Cl3Al · OPBr3, Br3Al · OPBr3, Cl3Ga · OPCl3, Cl3In · OPCl3, Cl3Tl · 2 OPCl3 are reported. The observed bond frequencies have been assigned. It is concluded that in all cases the addition occurs through the oxygen atoms of the phosphoroxidehalides. This follows from the strong negative shifts of the PO bond frequencies. The force constants kPO and kBO have been calculated using a simplified equation. With increasing atomic weight the interaction between halide and phosphoroxidechloride is diminished. The attempt to prepare the compound Cl3B · SPCl3 failed.

C. Djordjević

Papers

Metal-oxygen vibration modes in the infra-red spectra of aluminium, gallium and indium tris-acetylacetonates