Computational Investigation of the Bonding in [(η⁵–Cp′)₃(η¹–Cp′)M]^1– (M = Pu, U, Ce)

Abstract

displays a significantly longer η 1 −Cp′ distance in the solid state compared to the U 3+ and Pu 3+ analogues. To better understand this observation, a theoretical investigation was undertaken to examine the differences in bonding between the actinides 1-Pu and 1-U and how they compare with 1-Ce. The results show that although the bonding is largely ionic and dominated by ligand (2p)−metal (6d/ 5d) interactions, the polarization of 5f orbitals plays a significant role for 1-Pu and 1-U compared to the 4f-orbitals of 1-Ce. The lack of Ce(4f) interactions is compensated for by increased participation of the Ce(5d) orbitals relative to the actinide 6d orbitals, particularly for the σ-bound η 1 −Cp′ ligand. The use of multiple theoretical approaches including topological, localization, and energy decomposition approaches shows that 1-Pu and 1-U are very similar in covalent character compared to 1-Ce, though the composition and energy of the different interactions suggest that 1-U presents the strongest overall interactions.

Transformation of Mononuclear Plutonium(III) Tetrazolate Complexes into Dinuclear Complexes in the Solid State

“…Among the more exciting developments of the past decade of actinide chemistry has been an expansion of our understanding of the nature of chemical bonding in this series. − The more radially extended Frontier orbitals of actinides compared with those of lanthanides can lead to the formation of partially covalent bonds with a variety of ligands. When this is combined with the pronounced relativistic effects present in the 5f series, deviation from analogous 4f elements is often noted. , As a consequence of this, An III cations can exhibit larger bond enthalpies to coordinating ligands than measured with Ln III cations .…”

Employing a template synthesis to access diastereopure Np(iv) and U(iv) complexes and analysis of their 5f orbitals in bonding

“…59,60 Bonding. The natural localized molecular orbital (NLMO) representation has proven valuable in analyzing An-ligand interactions [61][62][63][64] and was first employed here to gain a localized chemical bonding picture of complexes 1-4. The goal was to study the effect of coordinating the indenide or the dtbpy ligand on the f-orbital participation of the metal.…”

Light‐, Middle‐ and Heavy‐Lanthanide Ate‐Complexes Bearing Ln(III)–Si bonds: Structural, Spectroscopic, and Bonding Analysis

“…[ 1‐2 ] Recent experimental and computational studies of organolanthanide complexes have done much to promote our cognition of their structure, spectral feature, optical and magnetic property, and reactivity. [ 3‐9 ] However, the coordinating atoms of the ligands used in these complexes are largely dominated by light p ‐block elements, such as fluorine, oxygen and nitrogen, as a consequence of the hard acid nature of lanthanide(III) (Ln(III)) ions. [ 4 ] In contrast, researches on organolanthanide complexes bearing heavier ligands are still less mature to date.…”