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Open AccessDissertation10.25959/23231156

The synthesis and decomposition behaviour of methylpalladium (II) N-heterocyclic carbene complexes

A.M. Magill-2005-01-01-UTAS Research Repository
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TL;DRAbstract

This thesis describes the synthesis of methylpalladium(II) complexes bearing various N-heterocyclic carbene (NHC) ligands. The decomposition behaviour of a subset of these complexes is also studied. The catalytic performance of methylpalladium(II) complexes bearing NHC ligands of similar steric bulk but varying basicities was assessed. Palladium(II) complexes bearing two large NHCs were found to be inactive in the Heck reaction of 4-bromoacetophenone and n-butyl acrylate, while methylpalladium(II) carbene dimers bearing bridging halide groups were found to be active pre-catalysts. Ligand basicity was shown, in some cases, to dramatically influence catalytic activity. In addition, the catalytic activity of [Pd(NHC)Me(PP)J13F4-type complexes was assessed. Such complexes were also found to be inactive.

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This thesis describes the synthesis of methylpalladium(II) complexes bearing various N-heterocyclic carbene (NHC) ligands. The decomposition behaviour of a subset of these complexes is also studied. The catalytic performance of methylpalladium(II) complexes bearing NHC ligands of similar steric bulk but varying basicities was assessed. Palladium(II) complexes bearing two large NHCs were found to be inactive in the Heck reaction of 4-bromoacetophenone and n-butyl acrylate, while methylpalladium(II) carbene dimers bearing bridging halide groups were found to be active pre-catalysts. Ligand basicity was shown, in some cases, to dramatically influence catalytic activity. In addition, the catalytic activity of [Pd(NHC)Me(PP)J13F4-type complexes was assessed. Such complexes were also found to be inactive.

Keywords

CarbeneChemistryCatalysisSteric effectsHalideLigand (biochemistry)DecompositionAcrylate

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