Diane Dickie - Synthesis, Lanthanide Coordination Chemistry, and Liquid-Liquid Extraction Performance of CMPO-Decorated Pyridine and Pyridine N-Oxide Platforms.

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      Rosario-Amorin, Daniel, Ouizem, Sabrina, Dickie, Diane A., Wen,   Yufeng, Paine, Robert T., Gao, Jian, Grey, John K., de   Bettencourt-Dias, Ana, Hay, Benjamin P., Delmau, Laetitia H.   Inorganic Chemistry 52 (6) 3063-3083

      Abstract: Syntheses for a set of new ligands   contg. one or two carbamoylmethylphosphine oxide (CMPO) fragments   appended to pyridine and pyridine N-oxide platforms are   described. Mol. mechanics analyses for gas phase   lanthanide-ligand interactions for the pyridine N-oxides indicate   that the trifunctional NOPOCO mols.,   2-{[Ph2P(O)][C(O)NEt2]C(H)}C5H4NO (7) and   2-{[Ph2P(O)][C(O)NEt2]CHCH2}C5H4NO (8), and pentafunctional   NOPOP'O'COC'O' mols., 2,6-{[Ph2P(O)][C(O)NEt2]C(H)}2C5H3NO (9)   and 2,6-{[Ph2P(O)][C(O)NEt2]CHCH2}2C5H3NO (10), should be able to   adopt, with minimal strain, tridentate and pentadentate chelate   structures, resp. As a test of these predictions, selected   lanthanide coordination chem. of the N-oxide derivs. was   explored. Crystal structure analyses reveal the formation of a   tridentate NOPOCO chelate structure for a 1:1 Pr(III) complex   contg. 7 while 8 adopts a mixed bidentate/bridging monodentate   POCO/NO binding mode with Pr(III). Tridentate and tetradentate   chelate structures were obtained for several 1:1 complexes of 9   while a pentadentate chelate structure is obsd. with 10. Emission   spectroscopy for one complex, [Eu(9)(NO3)3], in methanol, shows   that the Eu(III) ion resides in a low-symmetry site. Lifetime   measurements for methanol and deuterated methanol solns. indicate   four methanol mols. in the inner coordination sphere of the metal   ion, in addn. to the ligand, with the nitrate anions most likely   dissocd. The solvent extn. performance of 7-10 in   1,2-dichloroethane for Eu(III) and Am(III) in nitric acid solns.   was analyzed and compared with the performance of   2,6-bis(di-n-octylphosphinoylmethyl)pyridine N-oxide (TONOPOP'O')   and n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide   (OPhDiBCMPO) measured under identical conditions. [on   SciFinder(R)]

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