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: [(η(5)-C(5)H(5))(2)(THF)LuRu(η(5)-C(5)H(5))(CO)(2)], [(η(5)-C(5)Me(5))(2)(I)ThRu(η(5)-C(5)H(5))(CO)(2)], [(η(5)-C(5)H(5))(2)YRe(η(5)-C(5)H(5))(2)], [{N(CH(2)CH(2)NSiMe(3))(3)}URe(η(5)-C(5)H(5))(2)], [Y{Ga(NArCh)(2)}{C(PPh(2)NSiH(3))(2)}(CH(3)OCH(3))(2)], [{N(CH(2)CH(2)NSiMe(3))(3)}U{Ga(NArCH)(2)}(THF)], [(η(5)-C(5)H(5))(3)UGa(η(5)-C(5)Me(5))], [Yb(η(5)-C(5)H(5)){Si(SiMe(3))(3)(THF)(2)}], [(η(5)-C(5)H(5))(3)U(SnPh(3))], [(η(5)-C(5)H(5))(3)U(SiPh(3))], and (Ph[Me]N)(3)USi(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.

Structure and Magnetization Dynamics of Dy−Fe and Dy−Ru Bonded Complexes

“…There is precedence for utilizing the QTAIM model [14] to describe aspects of heterometallic interactions in Ln À TM bonded complexes computationally. [15] Accordingly,w eu sed DFT calculations to obtain relevant parameters.Our analysis was carried out using the Gaussian09 [16] (BP86; [17] Dy:c c-pVTZ-DK3 (all electron); [18] Ru [19] or Fe : [20] cc-pVTZ-DK (all electron);6-311G(d)) [21] and ADF [22] (BP86;TZ2P;ZORA) software packages.Both packages were used for calculations on the experimentally observed molecular geometries of 1 and 2 from single-crystal X-ray diffraction, and the geometries were optimized with the ADF package (Table S3). In all cases,w eo bserved critical points along the lines between Dy and Fe or Dy and Ru (LCPs; Figure 2).…”

Theoretical Investigation on Multiple Bonds in Terminal Actinide Nitride Complexes

“…This method has been used for actinide compounds and could provide good trends with the strength of chemical bonds. 27 QTAIM, a chemical bond is defined by the presence of a line of maximum ρ(r) along a bond path between two atoms and BCP. Therefore, the topological analysis of electron density could provide valuable information about the properties of the bond.…”

De Novo Design of an Endohedral Heteronuclear Dimetallofullerene (UGd)@C60 with Exceptional Structural and Electronic Properties

“…[29] MÀM bonds are both rare and difficult to synthesize in f-block elements. [32,33] To the best of our knowledge, no heteronuclear MÀM bond containing two f-elements has been reported yet. [32,33] To the best of our knowledge, no heteronuclear MÀM bond containing two f-elements has been reported yet.…”