Initiation Steps for the Polymerization of Vinyl Ethers Promoted by Cationic Palladium Aqua Complexes
Resource
Organometallics 21 (24): 5382-5385
Journal
Organometallics
Journal Volume
21
Journal Issue
24
Pages
5382-5385
Date Issued
2002
Date
2002
Author(s)
Abstract
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 [(P∼N)PdMe(H2O)]BF4 (P∼N = o-C6H4(PPh2)(N=CHAr)) promote the reaction via proton-transfer initiation. Insertion of vinyl ether into the Pd - Me bond in [(P∼N)PdMe(H2O)]BF4 does not proceed, but the single insertion of the same substrate into the Pd - acetal bond of [(P∼N)PdCOCH3(L)]BF4 provides the stable inserted product [(P∼N)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.
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Type
journal article
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