The behaviour of beryllium μ4-oxo-μ-carboxylates under electron impact

The electron impact mass spectra of eight polynuclear beryllium complexes Be₄O(RCO₂)₆ (R?H, CH₃, C₂H₅) and Be₄O(RCO₂)₅OR′ (R?CH₃, R′?H, CH₃, C₂H₅, C₃H₇; R?C₂H₅, R′?C₂H₅) are reported. The major fragmentations involve the elimination of (RCO)₂O (RCOOR′) or Be(RCO₂)₂ (Be(RCO₂)OR′) from the ions [M? L]⁺ and of {(R? H)CO}, (R′? H), H₂O and BeO from the lighter ions. The fragmentation patterns are practically independent of the organic groups present and can be rationalized by stereochemical considerations.     

A mass spectrometric study of halogenated beryllium μ4-oxohexa-μ-acetates

The electron impact mass spectra of Be₄O(CHal₃CO₂)₆ (Hal = F, Cl) are reported. The compounds give two series of fragment ions, [Be₄OL_x]⁺ and [Be₄OL₊]⁺, where L is an intact ligand or its fragmentation product. The major ligand dissociation path is the elimination of CHal₂CO₂ with halogen transfer to the metal. Other processes of importance are the loss of acid anhydride fragments, CF₂ with fluorine shift to the carboxyl group carbon atom, and halogens. Trinuclear ions also undergo decarboxylation, e.g. to give [Be₂O(CHal₃CO₂)₂(CHal₃)]⁺. Both spectra contain comparatively intense peaks of double-charged ions. The fragmentation patterns are rationalized by stereochemical considerations.     

Mehrkernige Kobaltkomplexe. V. Präparative Herstellung von Tetrakis (äthylendiamin)-μ-peroxo-μ-amido- und μ-peroxo-μ-thiocyanatodikobalt (III)-Komplexen ausgehend von Tetrakis (äthylendiamin)bis-(ammin)-μ-peroxo-dikobalt (III)-tetraperchlorat

Polynuclear Cobalt Complexes. V. Preparation of tetrakis (ethylenediamine)-μ-peroxo-μ-amido and μ-peroxo-μ-thiocyanato-dicobalt (III) complexes starting from tetrakis (ethylenediamine)bis-(ammine)-μ-peroxo-dicobalt (III)-tetraperchlorate Racemic tetrakis (ethylenediamine)-μ-peroxo-μ-amido-dicobalt (III) thiocyanate and its corresponding hydroperoxo- and superoxo-complexes have been isolated from [(en)₂(NH₃)Co(O₂)(NH₃)(en)₂](ClO₄)₄. A new binuclear peroxo complex containing thiocyanate as bridging ligand was prepared by the same method. The stretching frequencies of the CN- and CS-group as well as the NCS-bending frequence in the IR. spectrum of [(en)₂Co(O₂, SCN)Co(en)₂](NO₃)₃ suggest that the μ-thiocyanato group is N-bonded (2050, 750, 475 cm^?1). A comparison of IR. spectra of known singly and doubly bridged μ-peroxo complexes is made. Characteristic absorption bands, assignable to ν(O? O) and ν(Co? O) are given.     

Mass spectrometric study of μ4-oxohexa-μ-acetatotetrazinc,Zn4O(CH3CO2)6

The electron impact mass spectrum of Zn₄O(CH₃CO₂)₆ isostructural to Be₄O(CH₃CO₂)₆ studied earlier is reported. The principal fragmentation paths of both compounds involve the elimination of M(CH₃CO₂)₂ where M is Zn, Be, or (CH₃CO)₂O. Further fragmentations proceed by the losses of CH₂CO and H₂O. The spectrum of Zn₄O(CH₃CO₂)₆ contains intense doubly charged ions. The results obtained are interpreted in terms of stereochemical considerations.     

Oligomere μ-Imidophosphorsäurechloride und -amide

Oligomeric μ-Imidophosphoric Acid Chlorides and Amides Oligomeric μ-imidophosphoric acid chlorides. Cl₂(O)P? [NH? P(O)Cl]_n? Cl, (n = 1, 2, 3) are obtained by solvolysis of the linear phosphorylchlorphosphazenes, Cl₂(O)P? [N?PCl₂]_n? Cl, with the stoichiometric amount of anhydrous formic acid. The chlorides react with ammonia forming the amides. The amides are characterized by paper and gel chromatography. Course and rate of hydrolysis of diimidotriphosphoric acid pentaamide depend on pH.