Zinc(II) Hexafluoroacetylacetonate Complexes of Alkoxyamines: NMR and Kinetic Investigations. First Step for a New Way to Prepare Hybrid Materials.

A series of Zn(hfac)₂ alkoxyamines (diethyl(2,2-dimethyl-1-(tert-butyl-(1-pyridylethoxy)amino)propyl)phosphonate) coordinated at ortho, meta and para positions of their pyridyl moiety were prepared and their homolysis rate constants k_d measured. Up to a 30-fold increase in k_d was observed for the meta-(Zn-RR/SS) and para-(Zn-RR/SS) regioisomers. Moreover, the activation is also controlled by the amount of pyridine, used as a ligand competitor. XRD, ¹H and ³¹P NMR spectra show very different structures for each complexes in solid state and in solution depending on the diastereosiomers and on the regioisomers.