(NHC)-Pd(II) complexes with hydrophilic nitrogen ligands: catalytic properties in neat water

Abstract

The cleavage reactions of the dimers [(NHC)PdX2 ] 2 with hydrophilic N-donors, L, a?orded the mixedligand complexes of the type trans-[(NHC)LPdX2 ] (X = Cl or Br; NHC = 1,3-dialkylbenzimidazol-2-ylidene (BIm) or bis(imino)acenaphthene-annulated bis(2,6-diisopropylphenyl)imidazol-2-ylidene (BIAN-IPr); L = diethanolamine (DEA), morpholine (MOR), and 3-pyridinecarboxylic acid (3-PCA)). The new complexes (1{3) were characterized by elemental analysis and spectroscopic methods and the molecular structure of 1a was determined by X-ray di?raction studies. These complexes were applied in the Suzuki{Miyaura cross-coupling reaction of phenylboronic acid with aryl halides in neat water. The activities of catalysts were monitored by gas chromatography{ ame ionization detector and nuclear magnetic resonance. Whereas the complexes with DEA or 3-PCA ligands did not show signi?cant di?erence in the activity, the BIAN-IPr complexes 1b and 3b bearing DEA and 3-PCA, displayed the highest catalytic activity at 100C.

The cleavage reactions of the dimers [(NHC)PdX2 ] 2 with hydrophilic N-donors, L, a?orded the mixedligand complexes of the type trans-[(NHC)LPdX2 ] (X = Cl or Br; NHC = 1,3-dialkylbenzimidazol-2-ylidene (BIm) or bis(imino)acenaphthene-annulated bis(2,6-diisopropylphenyl)imidazol-2-ylidene (BIAN-IPr); L = diethanolamine (DEA), morpholine (MOR), and 3-pyridinecarboxylic acid (3-PCA)). The new complexes (1{3) were characterized by elemental analysis and spectroscopic methods and the molecular structure of 1a was determined by X-ray di?raction studies. These complexes were applied in the Suzuki{Miyaura cross-coupling reaction of phenylboronic acid with aryl halides in neat water. The activities of catalysts were monitored by gas chromatography{ ame ionization detector and nuclear magnetic resonance. Whereas the complexes with DEA or 3-PCA ligands did not show signi?cant di?erence in the activity, the BIAN-IPr complexes 1b and 3b bearing DEA and 3-PCA, displayed the highest catalytic activity at 100C.