Jump to main content
Jump to site search

Issue 12, 2018
Previous Article Next Article

Metal Acetylacetonate–Bidentate Ligand Interaction (MABLI) as highly efficient free radical generating systems for polymer synthesis

Author affiliations

Abstract

Metal Acetylacetonate–Bidentate Ligand Interaction (MABLI) is presented here as a new chemical mechanism for the highly efficient generation of free radicals for polymer synthesis. This MABLI process involves simultaneous ligand exchange and a change of the metal oxidation degree and is associated with the efficient release of free radicals. In conventional redox two-component radical generating systems, two criteria are required to be efficient: (1) oxidizing agents must exhibit a low bond dissociation energy (BDE) i.e. they are usually unstable (e.g. peroxides) and (2) a small difference must exist between the oxidation potential of the reducing agent and the reduction potential of the oxidation agent. In contrast, here, the criteria for efficient MABLI radical generation were energetic and geometric for both bidentate ligands and metal acetylacetonates. The strength of this approach is to use stable compounds in 2-components free radical initiating systems and to generate carbon centered radicals. Mechanistic investigations demonstrated the formation of new metal adducts by means of high-resolution mass spectroscopy (HR-ESI-MS) as well as UV-vis spectrometry. As a result of its high radical generating rate, the potential of MABLI was illustrated on the methacrylate free radical polymerization under mild conditions (room temperature, in air) and initiated with a small amount of metal acetylacetonate though it opens new perspectives for acac-like additions in organic chemistry.

Graphical abstract: Metal Acetylacetonate–Bidentate Ligand Interaction (MABLI) as highly efficient free radical generating systems for polymer synthesis

Back to tab navigation

Supplementary files

Publication details

The article was received on 10 Feb 2018, accepted on 26 Feb 2018 and first published on 27 Feb 2018


Article type: Communication
DOI: 10.1039/C8PY00238J
Citation: Polym. Chem., 2018,9, 1371-1378
  •   Request permissions

    Metal Acetylacetonate–Bidentate Ligand Interaction (MABLI) as highly efficient free radical generating systems for polymer synthesis

    P. Garra, F. Morlet-Savary, B. Graff, F. Dumur, V. Monnier, C. Dietlin, D. Gigmes, J. P. Fouassier and J. Lalevée, Polym. Chem., 2018, 9, 1371
    DOI: 10.1039/C8PY00238J

Search articles by author

Spotlight

Advertisements