The synthesis of water-soluble rhodium(I) salicylaldiminato and salicylhydrazonic complexes has been achieved employing two preparative routes. Schiff base condensation between 6A-deoxy-6A-amino-β-CD or 6A-deoxy-6A-hydrazino-β-CD and 5-sodiosulfonato-2-hydroxybenzaldehyde (sulfonated salicylaldehyde) (1) or 5-sodiosulfonato-3-tert-butyl-2-hydroxybenzaldehyde (sulfonated tBu-salicylaldehyde) (2) led to the formation of the corresponding imine or hydrazone ligands (3, 4, 5 and 6). Reaction of [Rh(COD)2+BF4−] with these new ligands in an alkaline solution formed the corresponding rhodium complexes quantitatively. These rhodium(I) complexes could also be prepared in one-pot by mixing, in stoichiometric proportions, the modified β-CDs with the sulfonated salicylaldehyde and with the rhodium precursor in an alkaline solution at room temperature. These rhodium complexes were applied as catalysts in the aqueous biphasic hydroformylation of 1-decene as a model reaction.
Melamine based polymer (MT) was prepared and then reacted with a mixture of glucose (Glu) and β-cyclodextrin (CD) under hydrothermal conditions to afford, MT/Glu-CD. Then, the adsorption of Pd salt was realized on MT/Glu-CD. The resulting compound was subsequently carbonized to furnish Pd/MT/C that exhibited high catalytic activity for the hydrogenation of nitroarenes in aqueous media. To elucidate the roles of CD, Glu, the molar ratio of Glu:CD and the carbonization in the catalytic activity, several control catalysts have been prepared and their performances for a model hydrogenation reaction were compared with that of Pd/MT/C. The results confirmed the importance of the carbonization as well as the presence of CD for achieving high catalytic activity. Moreover, it was found that the molar ratio of Glu:CD could affect the catalytic activity of the final catalyst and the optimum molar ratio of Glu:CD was 30:70. The recycling test as well as measurement of Pd leaching demonstrated high recyclability and low Pd leaching of Pd/MT/C.
In this article, a brief review of the recent functionalizations of the cage-like water-soluble phosphine 1,3,5-triaza-7-phosphaadamantane (PTA), involving N-quaternization (lower rim) and introduction of a side arm in C-6 position (upper rim) will be presented, highlighting selected examples in their use as ligands for ruthenium(II), iridium(I), and rhodium(I) moieties together with applications of the related complexes in homogeneous catalysis.