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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorLeavitt, Christopher M.en_US
dc.contributor.authorGresham, Garold L.en_US
dc.contributor.authorBenson, Michael T.en_US
dc.contributor.authorGaumet, Jean-Jacquesen_US
dc.contributor.authorPeterman, Dean R.en_US
dc.contributor.authorKlaehn, John R.en_US
dc.contributor.authorMoser, Meganen_US
dc.contributor.authorAubriet, Fredericen_US
dc.contributor.authorVan Stipdonk, Michael J.en_US
dc.contributor.authorGroenewold, Gary S.en_US
dc.identifier.citationInorganic chemistry. 2008 Apr 21; 47(8): 3056-64.en_US
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractDiphenyldithiophosphinate (DTP) ligands modified with electron-withdrawing trifluoromethyl (TFM) substitutents are of high interest because they have demonstrated potential for exceptional separation of Am (3+) from lanthanide (3+) cations. Specifically, the bis( ortho-TFM) (L 1 (-)) and ( ortho-TFM)( meta-TFM) (L 2 (-)) derivatives have shown excellent separation selectivity, while the bis( meta-TFM) (L 3 (-)) and unmodified DTP (L u (-)) did not. Factors responsible for selective coordination have been investigated using density functional theory (DFT) calculations in concert with competitive dissociation reactions in the gas phase. To evaluate the role of (DTP + H) acidity, density functional calculations were used to predict p K a values of the free acids (HL n ), which followed the trend of HL 3 < HL 2 < HL 1 < HL u. The order of p K a for the TFM-modified (DTP+H) acids was opposite of what would be expected based on the e (-)-withdrawing effects of the TFM group, suggesting that secondary factors influence the p K a and nucleophilicity. The relative nucleophilicities of the DTP anions were evaluated by forming metal-mixed ligand complexes in a trapped ion mass spectrometer and then fragmenting them using competitive collision induced dissociation. On the basis of these experiments, the unmodified L u (-) anion was the strongest nucleophile. Comparing the TFM derivatives, the bis( ortho-TFM) derivative L 1 (-) was found to be the strongest nucleophile, while the bis( meta-TFM) L 3 (-) was the weakest, a trend consistent with the p K a calculations. DFT modeling of the Na (+) complexes suggested that the elevated cation affinity of the L 1 (-) and L 2 (-) anions was due to donation of electron density from fluorine atoms to the metal center, which was occurring in rotational conformers where the TFM moiety was proximate to the Na (+)-dithiophosphinate group. Competitive dissociation experiments were performed with the dithiophosphinate anions complexed with europium nitrate species; ionic dissociation of these complexes always generated the TFM-modified dithiophosphinate anions as the product ion, showing again that the unmodified L u (-) was the strongest nucleophile. The Eu(III) nitrate complexes also underwent redox elimination of radical ligands; the tendency of the ligands to undergo oxidation and be eliminated as neutral radicals followed the same trend as the nucleophilicities for Na (+), viz. L 3 (-) < L 2 (-) < L 1 (-) < L u (-).en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesInorganic chemistryen_US
dc.relation.ispartofseriesInorg Chemen_US
dc.titleInvestigations of acidity and nucleophilicity of diphenyldithiophosphinate ligands using theory and gas-phase dissociation reactionsen_US
dc.coverage.spacialUnited Statesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2008 American Chemical Societyen_US

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