Designing the Ideal Uranyl Ligand: a Sterically-Induced Speciation Change in Complexes with Thiophene-Bridged Bis(3-hydroxy-N-methylpyridin-2-one)

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Structural characterization of a mononuclear uranyl complex with a tetradentate, thiophene-linked bis(3-hydroxy-N-methylpyridin-2-one) ligand reveals the most planar coordination geometry yet observed with this ligand class. The introduction of ethylsulfanyl groups onto the thiophene linker disrupts this planar, conjugated ligand arrangement, resulting in the formation of dimeric (UO{sub 2}){sub 2}L{sub 2} species in which each ligand spans two uranyl centers. Relative energy calculations reveal that this tendency toward dimer formation is the result of steric interference between ethylsulfanyl substituents and linking amides.

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11489

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Szigethy, Geza & Raymond, Kenneth N. September 11, 2009.

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Structural characterization of a mononuclear uranyl complex with a tetradentate, thiophene-linked bis(3-hydroxy-N-methylpyridin-2-one) ligand reveals the most planar coordination geometry yet observed with this ligand class. The introduction of ethylsulfanyl groups onto the thiophene linker disrupts this planar, conjugated ligand arrangement, resulting in the formation of dimeric (UO{sub 2}){sub 2}L{sub 2} species in which each ligand spans two uranyl centers. Relative energy calculations reveal that this tendency toward dimer formation is the result of steric interference between ethylsulfanyl substituents and linking amides.

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11489

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  • Journal Name: Inorganic Chemistry; Journal Volume: 48; Journal Issue: 24

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  • Report No.: LBNL-2876E
  • Grant Number: DE-AC02-05CH11231
  • DOI: 10.1021/ic901815b | External Link
  • Office of Scientific & Technical Information Report Number: 993493
  • Archival Resource Key: ark:/67531/metadc1013105

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  • September 11, 2009

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  • Oct. 14, 2017, 8:36 a.m.

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  • Oct. 17, 2017, 8:09 p.m.

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Szigethy, Geza & Raymond, Kenneth N. Designing the Ideal Uranyl Ligand: a Sterically-Induced Speciation Change in Complexes with Thiophene-Bridged Bis(3-hydroxy-N-methylpyridin-2-one), article, September 11, 2009; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc1013105/: accessed June 22, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.