M. Pereira, M. Pfeffer, M. Rotteveel
Oct 3, 1989
Citations
0
Influential Citations
22
Citations
Journal
Journal of Organometallic Chemistry
Abstract
The reaction between α-trimethylsilyl-8-methylquinoline and palladium acetate, followed by metathesis of the acetato groups with lithium chloride, gave a mixture of chloride-bridged cyclopalladated dimers [{PdCHRC9H6N(μ-Cl)}]2 (2, R H; 3, R SiMe3) through cleavage of a CSi and a CH bond, respectively. In the presence of internal alkynes, compound 2 gave a stable chloride-bridged dimer by insertion of one molecule of dimethyl acetylenedicarboxylate (DMAD) into its PdC bond, and a monomeric compound by regioselective insertion of two molecules of ethyl-3-phenylpropiolate (EPP) into its PdC bond. In contrast, the reactions of 3 with both DMAD and EPP gave organometallic compounds containing η3-allylic moieties; these were formed through insertion of the alkynes into the PdC bond of 3 followed by a 1,3-sigmatropic shift of the SiMe3 group to the terminal carbon atom of the C(3) unit bridging the quinoline ring and the palladium atom.