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Initiation Steps for the Polymerization of Vinyl Ethers Promoted by Cationic Palladium Aqua Complexes

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posted on 02.11.2002 by Chi-Li Chen, Yi-Chun Chen, Yi-Hong Liu, Shie-Ming Peng, Shiuh-Tzung Liu
Both deuterium-labeled experimental and NMR spectroscopic analyses of poly(vinyl ether) offer the mechanistic insight into the polymerization, indicating that the cationic palladium aqua imine−phosphine complexes [(PN)PdMe(H2O)]BF4 (PN = o-C6H4(PPh2)(NCHAr)) promote the reaction via proton-transfer initiation. Insertion of vinyl ether into the Pd−Me bond in [(PN)PdMe(H2O)]BF4 does not proceed, but the single insertion of the same substrate into the Pd−acetal bond of [(PN)PdCOCH3(L)]BF4 provides the stable inserted product [(PN)PdCH(OEt)CH2COCH3]BF4, which has been characterized by an X-ray structural determination. However, these palladium complexes do not catalyze the polymerization or copolymerization of vinyl ether and carbon monoxide.