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

Gerard Audran (1) , Elena Bagryanskaya (2) , Irina Bagryanskaya (2) , Mariya Edeleva (2) , Sylvain R.A. Marque (1) , Dmitriy Parkhomenko (2) , Evgeny Tretyakov (2) , Svetlana Zhivetyeva (2)

1 ICR - Institut de Chimie Radicalaire
2 RAS, SB, NN - Vorozhtsov Novosibirsk Institute of Organic Chemistry

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, H-1 and P-31 NMR spectra show very different structures for each complexes in solid state and in solution depending on the diastereosiomers and on the regioisomers.

Keywords: activation; alkoxyamines; C-ON bond homolysis; nitroxide-mediated polymerization; on bond homolysis; polymers; quaternization; rate enhancement; Zn(hfac)(2) complexes

Domains: Chemical Sciences

Gerard Audran, Elena Bagryanskaya, Irina Bagryanskaya, Mariya Edeleva, Sylvain R.A. Marque, et al.. Zinc(II) Hexafluoroacetylacetonate Complexes of Alkoxyamines: NMR and Kinetic Investigations. First Step for a New Way to Prepare Hybrid Materials. ChemistrySelect, 2017, 2 (12), pp.3584--3593. ⟨10.1002/slct.201700678⟩. ⟨hal-01774187⟩