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On the Nature of Actinide- and Lanthanide-Metal Bonds in Heterobimetallic Compounds

Vlaisavljevich, B.; Miró, P.; Cramer, C. J.; Gagliardi, L.; Infante, I.; Liddle, S. T.
Chem. Eur. J. 2011, 17, 8424 (doi:10.1002/chem.201100774)

Eleven experimentally characterized complexes containing heterobimetallic bonds between f-block and other elements were examined by quantum chemical methods: [(η5-C5H5)2(THF)LuRu(η5-C5H5)(CO)2], [(η5-C5Me5)2(I)ThRu(η5-C5H5)(CO)2], [(η5-C5H5)2YRe(η5-C5H5)2], [{N(CH2CH2NSiMe3)3}URe(η5-C5H5)2], [Y{Ga(NArCh)2}{C(PPh2NSiH3)2}(CH3OCH3)2], [{N(CH2CH2NSiMe3)3}U{Ga(NArCH)2}(CH3OCH3)], [(η5-C5H5)3UGa(η5-C5Me5)], [Yb(η5-C5H5){Si(SiMe3)3(THF)2}], [(η5-C5H5)3U(SnPh3)], [(η5-C5H5)3U(SiPh3)], and (Ph[Me]N)3USi(SiMe3)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.