Molecular complexes have been formed between two aliphatic nitroxides, di-tert-butyl nitroxide and 2,2,6,6-tetramethylpiperidine-N-oxyl, and group IV Lewis acids. Analysis of the epr spectra shows that in all cases 1:1 complexes are formed. The π-electron spin density of a nitroxide complex can be analyzed from its epr spectrum and changes in the nitroxide 14N hfs upon complexation are a measure of the acceptor strength of the Lewis acid. For the acids studied here the order of acceptor strength is TiCl4 > SnCl4 > SnBr4 > SiF4 ≳ Sn(t-Bu)2Cr(CO)5 ≈ SiCl4 ≳ GeCl4 ≈ Ti(OPh)4. In some cases epr spectra show the nitroxide and its complex to be in equilibrium and thermodynamic constants for complex formation are obtained.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry