What is the nature of the uranium()-arene bond?

• Published in: Chemical science (Cambridge) 2024-01, Vol.15 (5), p.181-1819
• Main Authors: Chowdhury, Sabyasachi Roy, Goodwin, Conrad A. P, Vlaisavljevich, Bess
• Format: Article
• Language: English
• Subjects: Bonding; Chemistry; Density functional theory; Electron density; Electronic structure; Electrons; Oxidation; Valence
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d3sc04715f

Complexes of the form [U(η 6 -arene)(BH 4 ) 3 ] where arene = C 6 H 6 ; C 6 H 5 Me; C 6 H 3 -1,3,5-R 3 (R = Et, iPr, t Bu, Ph); C 6 Me 6 ; and triphenylene (C 6 H 4 ) 3 were investigated towards an understanding of the nature of the uranium-arene interaction. Density functional theory (DFT) shows the interaction energy reflects the interplay between higher energy electron rich π-systems which drive electrostatic contributions, and lower energy electron poor π-systems which give rise to larger orbital contributions. The interaction is weak in all cases, which is consistent with the picture that emerges from a topological analysis of the electron density where metrics indicative of covalency show limited dependence on the nature of the ligand - the interaction is predominantly electrostatic in nature. Complete active space natural orbital analyses reveal low occupancy U-arene π-bonding interactions dominate in all cases, while δ-bonding interactions are only found with high-symmetry and electron-rich C 6 Me 6 . Finally, both DFT and multireference calculations on a reduced, formally U( ii ), congener, [U(C 6 Me 6 )(BH 4 ) 3 ] − , suggests the electronic structure ( S = 1 or 2), and hence metal oxidation state, of such a species cannot be deduced from structural features such as arene distortion alone. We show that arene geometry strongly depends on the spin-state of the complex, but that in both spin-states the complex is best described as U( iii ) with an arene-centred radical. Complexes of the form [U(η 6 -arene)(BH 4 ) 3 ] where arene = C 6 H 6 ; C 6 H 5 Me; C 6 H 3 -1,3,5-R 3 (R = Et, i Pr, t Bu, Ph); C 6 Me 6 ; and triphenylene (C 6 H 4 ) 3 were investigated towards an understanding of the nature of the uranium-arene interaction.