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Multiple Bonding in Lanthanides and Actinides: Direct Comparison of Covalency in Thorium(IV)- and Cerium(IV)-Imido Complexes.
Cheisson, Thibault; Kersey, Kyle D; Mahieu, Nolwenn; McSkimming, Alex; Gau, Michael R; Carroll, Patrick J; Schelter, Eric J.
Afiliação
  • Cheisson T; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
  • Kersey KD; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
  • Mahieu N; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
  • McSkimming A; Département de Chimie, ENS Paris-Saclay , Université Paris-Saclay , 94235 Cachan , France.
  • Gau MR; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
  • Carroll PJ; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
  • Schelter EJ; P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
J Am Chem Soc ; 141(23): 9185-9190, 2019 06 12.
Article em En | MEDLINE | ID: mdl-31117665
ABSTRACT
A series of thorium(IV)-imido complexes was synthesized and characterized. Extensive experimental and computational comparisons with the isostructural cerium(IV)-imido complexes revealed a notably more covalent bonding arrangement for the Ce═N bond compared with the more ionic Th═N bond. The thorium-imido moieties were observed to be 3 orders of magnitude more basic than their cerium congeners. More generally, these results provide unique experimental evidence for the larger covalent character of 4f05d0 Ce(IV) multiple bonds compared to its 5f06d0 Th(IV) actinide congener.
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2019 Tipo de documento: Article
Texto completo
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2019 Tipo de documento: Article