Evaluation of the malonamide substructure with respect to binding site preorganization and complementarity for lanthanide metal ions suggests a new ligand architecture specifically designed to enhance lanthanide ion affinity. Consideration of conformational reorganization, restricted bond rotation, and donor group orientation suggests that typical malonamide structures, for example, N,N,N'N'-tetrahexylpropane-1,3-diamide (1), N,N'-dibutyl-N,N'-dimethyl-2-tetradecylpropane-1,3-diamide (2), or N,N,N'N'-tetramethylpropane-1,3-diamide (6), are poorly organized for metal ion complexation. Molecular mechanics analyses show that the unfavorable enthalpic and entropic terms are eliminated by the use of the novel bicyclic architecture found in 3,9-diaza-3,9-dimethylbicyclo[4.4.0]decane-2,10-dione (7). Diamide 7 was prepared, and the X-ray crystal structure of the complex [Eu(7)(2)(NO(3))(3)] exhibits the same chelate conformation predicted by the molecular mechanics model. A hydrophobic derivative, 3,9-diaza-3,9-dioctylbicyclo[4.4.0]decane-2,10-dione (8), was prepared, and solvent extraction studies reveal that the preorganized architecture of 8 gives a dramatic enhancement in binding affinity, exhibiting Eu(3+) distribution coefficients that are 7 orders of magnitude larger than a typical malonamide ligand, 1.

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Metal- halogen exchange of vinylcyclopropene 4 followed by addition of [(Me3P)2Ir(CO)Cl] produced iridabenzvalene 5. The metallabenzene valence isomer was characterized by NMR and IR spectroscopy and by X-ray crystallography. Isomerization of complex 5 to iridabenzene derivatives 6 and 13 was accomplished by thermolysis and by Ag+ ions, respectively. The former transformation was a clean and quantitative process that displayed first-order kinetics.

Seven new iridabenzenes were prepared by the addition of (Z)-1,2-diphenyl-3-(2-lithioethenyl)-1-cyclopropene to the Vaska-type complexes [IrCl(CO)(PR 3 ) 2 ], containing differing phosphine ligands. The iridabenzenes could be isolated from the reaction mixture either by direct means or after heating of the crude solution. In the case of the reactions using PMe 3 and PEt 3 , a σ-vinyl/η 2 -cyclopropene Ir(I) complex, best described as an iridabenzvalene, could be isolated and fully characterized. The metallabenzvalene intermediate could be cleanly converted to the corresponding iridabenzene by heating in solution. The PEt 3 -substituted iridabenzene and iridabenzvalene were characterized by X-ray crystallography. Plausible mechanisms for the formation of both iridacycles from the lithiated vinylcyclopropene as well as the isomerization of the benzvalene into the benzene are postulated.

A new bicyclic diamide compound, 3,9-diaza-3,9-dioctylbicyclo[4.4.0]decane-2,10-dione (1) has been prepared, and its affinity for Eu 3þ and Am 3þ has been explored using liquid-liquid extraction methods. Molecular mechanics calculations have shown that the two amide oxygen atoms in 1 should be ideally situated for binding to trivalent actinide or lanthanide ions and should form strong complexes. The data in this report support this hypothesis. As determined by liquid-liquid extraction, the affinity of 1 for Eu 3þ is on the order of 10 7 times greater than previously investigated malonamides. The extraction behavior for Am 3þ is similar to that of Eu 3þ .