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

Gérard Audran, Elena Bagryanskaya, Irina Bagryanskaya, Mariya Edeleva, Sylvain R.A. Marque, Dmitriy Parkhomenko, Evgeny Tretyakov, Svetlana Zhivetyeva

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

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 kd measured. Up to a 30-fold increase in kd 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.

Original languageEnglish
Pages (from-to)3584-3593
Number of pages10
JournalChemistrySelect
Volume2
Issue number12
DOIs
Publication statusPublished - 24 Apr 2017

Keywords

  • activation
  • alkoxyamines
  • C−ON bond homolysis
  • rate enhancement
  • Zn(hfac) complexes
  • NITROXIDE-MEDIATED POLYMERIZATION
  • POLYMERS
  • C-ON bond homolysis
  • ON BOND HOMOLYSIS
  • QUATERNIZATION
  • Zn(hfac)(2) complexes

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