On the nature of actinide- and lanthanide-metal bonds in heterobimetallic compounds

Bess Vlaisavljevich, Pere Mirõ, Christopher J. Cramer, Laura Gagliardi, Ivan Infante, Stephen T. Liddle

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Abstract

Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f-block and other elements were examined by quantum chemical methods: [(η5-C5H 5)2(THF)LuRu(η5-C 5H5) (CO)2], [(η5- C5Me5)2(I)ThRu(η5- C5H5) (CO)2], [(η5- C5H5)2YRe(η5-C 5H5)2], [{N(CH2CH 2NSiMe3)3}URe(η5- C5H5)2], [Y{Ga(NArCh)2}{C(PPh 2NSiH3)2}(CH3OCH3) 2], [{N(CH2CH2NSiMe3) 3}U{Ga(NArCH)2}(THF)], [(η5- C5H5)3UGa(η5-C 5Me5)], [Yb(η5-C 5H5){Si(SiMe3)3(THF)2}], [(η5-C5H5)3U(SnPh 3)], [(η5-C5H5) 3U(SiPh3)], and (Ph[Me]N)3USi(SiMe 3)3. Geometries in good agreement with experiment were obtained at the density functional level of theory. The multiconfigurational complete active space self-consistent field method (CASSCF) and subsequent corrections with second order perturbation theory (CASPT2) were applied to further understand the electronic structure of the lanthanide/actinide-metal (or metal-metalloid) bonds. Fragment calculations and energy-decomposition analyses were also performed and indicate that charge transfer occurs from one supported metal fragment to the other, while the bonding itself is always dominated by ionic character.

Original languageEnglish (US)
Pages (from-to)8424-8433
Number of pages10
JournalChemistry - A European Journal
Volume17
Issue number30
DOIs
StatePublished - Jul 18 2011

Keywords

  • actinides
  • density functional calculations
  • energy-decomposition analysis
  • lanthanides
  • metal-metal bonds

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