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

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. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.