Macrocyclic multidentate ligands for metal ion complexation
Pugia, Michael Joseph
MetadataShow full item record
Synthetic methods for the preparation of novel multidentate ligands and the assessment of metal ion complexation by these ligands are described in this dissertation. The molecular structure of the multidentate ligands is systematically varied to provide a better understanding of the process of molecular complexation. Crowns ethers (macrocyclic polyethers) with a hydroxyl and an alkyl group linked directly to the central carbon of a three carbon bridge are synthesized in one step reactions of glycol and bisphenol dianions with substituted epichlorohydrins. Crown ethers bearing two hydroxymethyl functions are prepared from benzyl-protected and allyl-protected precursors. Synthetic pathways have been established for the preparation from crown ether alcohols of crown ethers with lonizable sulfonic, phosphonic and carboxylic acid pendant arms. Neutral amide- and ester-containing pendant arms are attached to crowns by reactions with crown acid chlorides. A series of novel bis-crown ethers result from condensations of diacid chlorides with crown alcohols. Acyclic tropolone ligands are prepared by reaction of calcium tropolone with 1,3-ditosyloxypropanes.