| In this thesis, the synthesis, characterization and crystal structures of a series of new adducts of2-pyrazinylferrocene cyclopalladated complexes,6-chloro-4-pyrimidinylferrocene cyclopalladated complexes and2,4-dichloro-6-pyrimidinyl ferrocene complexes were reported. These complexes have been successfully used in palladium-catalyzed the Suzuki and Sonogashira reactions.1. Five new adducts of cyclopalladated pyrazinylferrocene1-5were synthesized obtained from the cyclopalladation reactions and bridge-splitting reactions. Then the adducts of palladacycles6-10prepared through anion exchange reactions with Nal in acetone (Scheme1). Pyrimidinylferrocene ligands11-13have been synthesized by C-C and C-N coupling. The new cyclopalladated complexes14,15and16were also synthesized via stepwise coupling reactions (Scheme2). Pyrimidinyl ferrocene17,18and19were successfully synthesized by palladium-catalyzed the Suzuki reactions (Scheme3). Their detailed structures were determined by’H NMR, IR and single-crystal X-ray analysis. 2. The new ferrocenyl palladium complexes14,21-23,25-26,28a-29b have been prepared and characterized. Their catalytic activity were evaluated in the coupling reactions.Complex14was found very efficient for the Suzuki coupling reaction of aryl chlorides with aryl boronic acids.Palladacycles21-23were found efficient catalysts for the Sonogashira reaction of ary1bromides and some activated aryl chlorides under copper-and amine-free conditions. Two air-stable N-heterocyclic carbene (NHC) adducts of cyclopalladated ferrocenylpyridine containing chlorine/iodine anion have been successfully applied to the coupling of terminal alkynes with arylboronic acids under atmospheric conditions. Palladacycle26showed slightly more activity for the reaction.Four new triphenylphosphine adducts of palladacycles28-31containing chlorine/iodine anion have been prepared and characterized. Halogen anions have different effects on the catalytic activity in the reactions. |
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