Synthesis of α-, β-, and γ-Ketophosphonate Polymer-Supported Reagents:  The Role of Intra-ligand Cooperation in the Complexation of Metal Ions

Abstract

Bifunctional ligands, viz., α-, β-, and γ-ketophosphonic acids, wherein a carbonyl group is systematically separated from a phosphoryl group with methylene moieties, have been immobilized on cross-linked polystyrene beads via the Arbusov and Perkow reactions. Studies with Eu(III), Cu(II), Pb(II), Cd(II), Co(II), and Ag(I) in various acid solutions show that under conditions where coordination is the dominant mode of metal ion sorption, the α-ketophosphonate complexes greater levels of metal ions than the β-ketophosphonate and both complex far greater levels of ions than the γ-ketophosphonate. The latter performs in a manner comparable to the monofunctional phosphonic acid resin. The results are consistent with intra-ligand cooperation being an important factor in the design of polymer-supported reagents for the complexation of high levels of metal ions.

Monomers for adhesive polymers. XV. Synthesis, photopolymerization, and adhesive properties of polymerizable β-ketophosphonic acids

“…It has been demonstrated that β‐ketophosphonic acids are strong metal ion complexing agents . However, the synthesis of polymerizable β‐ketophosphonic acids and their evaluation in dental materials has, to the best of our knowledge, not been reported yet.…”

Immobilization of lithium-selective 14-crown-4 on crosslinked polymer supports

“…Ligands immobilized onto crosslinked polymers for the selective complexation of metal ions include bis(imidazol-2-yl)-methylaminomethane [13], 1-(2-aminoethyl)-piperazine [14], aminothiophosphonate [15], and ketophosphonates [16].…”

Development of a new ion-exchange/coordinating phosphate ligand for the sorption of U(VI) and trivalent ions from phosphoric acid solutions

“…Dicarboxylic acids form lanthanide and actinide complexes but the bound ions still form covalent bonds with soft donor atoms (Sasaki et al, 2006). Incorporating a carbonyl group into a supported phosphonic acid also improves its metal ion affinity (Alexandratos and Hussain, 1998). The uranyl affinities are thus best summarized in Fig.…”