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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
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 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
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Submitted on : Monday, April 23, 2018 - 2:41:47 PM
Last modification on : Friday, January 7, 2022 - 3:53:28 AM

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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, Wiley, 2017, 2 (12), pp.3584--3593. ⟨10.1002/slct.201700678⟩. ⟨hal-01774187⟩

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