Journal article
On the Nature of Actinide- and Lanthanide-Metal Bonds in Heterobimetallic Compounds
Chemistry : a European journal, Vol.17(30), pp.8424-8433
07/18/2011
DOI: 10.1002/chem.201100774
PMID: 21714020
Abstract
Eleven experimentally characterized complexes containing heterobimetallic bonds between elements of the f-block and other elements were examined by quantum chemical methods: [(eta(5)-C5H5)(2)(THF)LuRu(eta(5)-C5H5)(CO)(2)], [(eta(5)-C5Me5)(2)(I)ThRu(eta(5)-C5H5)(CO)(2)], [(eta(5)-C5H5)(2)YRe(eta(5)-C5H5)(2)], [{N(CH2CH2NSiMe3)(3)}URe(eta(5)-C5H5)(2)], [Y{Ga(NArCh)(2)}{C(PPh2NSiH3)(2)}(CH3OCH3)(2)], [{N(CH2CH2NSiMe3)(3)}U{Ga(NArCH)(2)}(THF)], [(eta(5)-C5H5)(3)UGa(eta(5)-C5Me5)], [Yb(eta(5)-C5H5){Si(SiMe3)(3)(THF)(2)}], [(eta(5)-C5H5)(3)U(SnPh3)], [(eta(5)-C5H5)(3)U(SiPh3)], and (Ph[Me]N)(3)USi(SiMe3)(3). Geometries in good agreement with experiment were obtained at the density functional level of theory. The multi-configurational 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.
Details
- Title: Subtitle
- On the Nature of Actinide- and Lanthanide-Metal Bonds in Heterobimetallic Compounds
- Creators
- Bess Vlaisavljevich - University of MinnesotaPere Miro - University of MinnesotaChristopher J. Cramer - University of MinnesotaLaura Gagliardi - University of MinnesotaIvan Infante - Donostia International Physics CenterStephen T. Liddle - University of NottinghamMaterials Science of Actinides (MSA)
- Resource Type
- Journal article
- Publication Details
- Chemistry : a European journal, Vol.17(30), pp.8424-8433
- Publisher
- Wiley
- DOI
- 10.1002/chem.201100774
- PMID
- 21714020
- ISSN
- 0947-6539
- eISSN
- 1521-3765
- Number of pages
- 10
- Grant note
- DE-SC0001089 / U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences; United States Department of Energy (DOE) CHE-0952054 / U.S. National Science Foundation; National Science Foundation (NSF) 0952054 / Division Of Chemistry; Direct For Mathematical & Physical Scien; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) Materials Science of Actinides Center EP/F030517/1; EP/G051763/1 / EPSRC; UK Research & Innovation (UKRI); Engineering & Physical Sciences Research Council (EPSRC) EP/G051763/1; EP/F030517/1 / Engineering and Physical Sciences Research Council; UK Research & Innovation (UKRI); Engineering & Physical Sciences Research Council (EPSRC) USDOE/DE-SC002183 / Office of Basic Energy Sciences, U.S. Department of Energy; United States Department of Energy (DOE)
- Language
- English
- Date published
- 07/18/2011
- Academic Unit
- Chemistry
- Record Identifier
- 9984618522502771
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