Unknown

Dataset Information

0

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


ABSTRACT: Complexes of the form [U(η6-arene)(BH4)3] where arene = C6H6; C6H5Me; C6H3-1,3,5-R3 (R = Et, iPr, tBu, Ph); C6Me6; and triphenylene (C6H4)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 C6Me6. Finally, both DFT and multireference calculations on a reduced, formally U(ii), congener, [U(C6Me6)(BH4)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.

SUBMITTER: Chowdhury SR 

PROVIDER: S-EPMC10829017 | biostudies-literature | 2024 Jan

REPOSITORIES: biostudies-literature

altmetric image

Publications

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

Chowdhury Sabyasachi Roy SR   Goodwin Conrad A P CAP   Vlaisavljevich Bess B  

Chemical science 20231214 5


Complexes of the form [U(η<sup>6</sup>-arene)(BH<sub>4</sub>)<sub>3</sub>] where arene = C<sub>6</sub>H<sub>6</sub>; C<sub>6</sub>H<sub>5</sub>Me; C<sub>6</sub>H<sub>3</sub>-1,3,5-R<sub>3</sub> (R = Et, iPr, <i>t</i>Bu, Ph); C<sub>6</sub>Me<sub>6</sub>; and triphenylene (C<sub>6</sub>H<sub>4</sub>)<sub>3</sub> 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 highe  ...[more]

Similar Datasets

| S-EPMC6024247 | biostudies-literature
| S-EPMC8362146 | biostudies-literature
| S-EPMC8036695 | biostudies-literature
| S-EPMC5974406 | biostudies-literature
| S-EPMC1162028 | biostudies-other
| S-EPMC11863384 | biostudies-literature
| S-EPMC8036253 | biostudies-literature
| S-EPMC2828042 | biostudies-literature
| S-EPMC6258733 | biostudies-literature
| S-EPMC3387120 | biostudies-literature