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Analytical chromatography with element-specific detection of inorganic compounds
Abstract
Capillary column GC-MIP was applied to trifluorinated gallium, indium, and copper $\beta$-diketonates, a tetradentate copper $\beta$-ketoaminate, ferroceneboronate derivatives of diols and cyclopentadienyl rhodium dicarbonyl. The chemically inert fused-silica capillary column showed improved GC characteristics for the metal chelates. Excellent GC characteristics of the organometallic compounds were observed. The MIP parameters for Ga, In, Cu, Rh, Fe and B elements were investigated and optimized. Detection limits and selectivities against carbon for these elements were determined. Gas chromatography with sensitive and element selective MIP detection was employed to study ligand exchange reactions between fluorinated gallium, indium, aluminum, copper and nickel $\beta$-diketonates which occurred in chloroform. The ligand exchange reactions between gallium chelates showed statistical redistribution of ligands. HPLC study of ligand exchange reactions between fluorinated gallium, indium, copper and nickel $\beta$-diketonates proved that these reactions could occur in liquid phase. The process of ligand exchange reaction between two fluorinated gallium $\beta$-diketonates (Ga(TFA)$\sb3$ and Ga(TTB)$\sb3$) was monitored and the kinetic parameters such as reaction rate constant and overall reaction order of this reaction were determined with HPLC. MIP detection proved valuable for GC analysis of diols through their ferroceneboronate derivatives. The response factors for both iron and boron specific detection were consistent for both pinacol and dicyclohexyl-1,1$\sp\prime$-diol ferroceneboronates. Pyrolysis-GC of tetradentate salicyladimine ligand and copper and nickel chelates was carried out to study the thermal fragmentation patterns of these materials. Mass spectrometric detection, as well as parallel FID and NPD detection, was employed. The use of a capillary column improved the peak shapes and resolution of the fragment compounds. The two major fragment compounds were phenol and o-methyl phenol. The central metal appeared to have little influence on the patterns of major fragment peaks.
Subject Area
Analytical chemistry
Recommended Citation
Wang, Tao, "Analytical chromatography with element-specific detection of inorganic compounds" (1990). Doctoral Dissertations Available from Proquest. AAI9022756.
https://scholarworks.umass.edu/dissertations/AAI9022756