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Synthesis and Structure of Imine–N-Heterocyclic Carbene Palladium Complexes and Their Catalytic Behavior in Norbornene Polymerization
On the basis of the steric effects of ligand, a series of imine–N-heterocyclic carbene (NHC) ligands and their corresponding five-membered palladium complexes with bulky substituents on both the imine and the NHC moieties were synthesized and characterized. Transpalladation of silver carbene complex...
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Published in: | Organometallics 2013-08, Vol.32 (16), p.4507-4515 |
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Main Authors: | , , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | On the basis of the steric effects of ligand, a series of imine–N-heterocyclic carbene (NHC) ligands and their corresponding five-membered palladium complexes with bulky substituents on both the imine and the NHC moieties were synthesized and characterized. Transpalladation of silver carbene complexes with (COD)PdCl2 and (COD)PdMeCl afforded the palladium dichloride and methylpalladium complexes, respectively. Bulky cationic palladium complexes were further obtained by treatment of the methylpalladium complexes with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBAF) in CH3CN. Well-defined cationic palladium complexes were confirmed by X-ray crystal diffraction to have trans forms. Palladium dichloride complexes and methylpalladium complexes after activation with MMAO show high activity for norbornene polymerization, whereas cationic palladium complexes can polymerize norbornene alone without any cocatalysts and exhibit a high thermostability. Norbornene polymerization with the cationic palladium catalyst was proven to proceed through a coordination–insertion mechanism by NMR studies. Analysis of oligomers obtained by polymerizing the monomer in the presence of H2 reveals the existence of a C7 linkage in the polynorbornene (PNB) by σ-bond metathesis, which may be the reason for the insolublity of polynorbornenes obtained by palladium catalysts. |
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ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/om400268y |