Jump to main content
Jump to site search

Issue 34, 2015
Previous Article Next Article

Polymeric palladium-mediated carbene polymerization

Author affiliations


A metalloenzyme-inspired polymeric palladium catalyst, which was prepared by self-assembly of a polymeric imidazole ligand with PdCl2, promoted carbene polymerization with high catalytic activity and reusability. Besides the atactic polycarbethoxycarbene (PCEC), a small amount of stereoregular PCEC was also obtained with poly(imidazole-Pd)-mediated polymerization of ethyl diazoacetate (EDA). This is the first example that a stereoregular polycarbene in an isolated form is obtained with a palladium-initiating system, suggesting that the steric polymeric imidazole ligand could affect the carbene insertion process. Detailed end group analyses on the obtained atactic and stereoregular PCEC revealed the chain initiation and chain termination mechanisms. XPS analyses on the oxidation state changes of the palladium center exhibited that PdII was reduced to PdI, which suggests that an intramolecular electron transfer process occurred during the interaction of palladium and EDA. Kinetic studies showed a zero order kinetic dependent on the concentration of EDA, which indicates a strong binding of EDA on the catalyst preceding carbene formation. With the addition of a radical inhibitor, the reaction rate was found to be greatly decreased. In the presence of a spin trap, a striking electron paramagnetic resonance (EPR) spectrum could be detected, which suggests the involvement of radical intermediates. DFT calculations on the proposed Pd-carbene radical species supported the EPR analyses, which assigned a significant amount of spin density on the carbene-carbon atom. Based on these results, we proposed an unprecedented metal-carbene radical polymerization mechanism, which occurs through a stepwise carbene radical migration and insertion process to afford polycarbenes.

Graphical abstract: Polymeric palladium-mediated carbene polymerization

Back to tab navigation

Supplementary files

Publication details

The article was received on 17 Jun 2015, accepted on 10 Jul 2015 and first published on 13 Jul 2015

Article type: Paper
DOI: 10.1039/C5PY00934K
Author version
Download author version (PDF)
Citation: Polym. Chem., 2015,6, 6163-6170

  •   Request permissions

    Polymeric palladium-mediated carbene polymerization

    F. Li, L. Xiao and L. Liu, Polym. Chem., 2015, 6, 6163
    DOI: 10.1039/C5PY00934K

Search articles by author