Journal article
What is the nature of the uranium(iii)-arene bond?
Chemical science (Cambridge), Vol.15(5), pp.1810-1819
01/31/2024
DOI: 10.1039/d3sc04715f
PMCID: PMC10829017
PMID: 38303954
Abstract
Complexes of the form [U(eta(6)-arene)(BH4)(3)] where arene = C6H6; C6H5Me; C6H3-1,3,5-R-3 (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 pi-systems which drive electrostatic contributions, and lower energy electron poor pi-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 pi-bonding interactions dominate in all cases, while delta-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.
Details
- Title: Subtitle
- What is the nature of the uranium(iii)-arene bond?
- Creators
- Sabyasachi Roy Chowdhury - University of South DakotaConrad A. P. Goodwin - University of ManchesterBess Vlaisavljevich - University of South Dakota
- Resource Type
- Journal article
- Publication Details
- Chemical science (Cambridge), Vol.15(5), pp.1810-1819
- Publisher
- Royal Soc Chemistry
- DOI
- 10.1039/d3sc04715f
- PMID
- 38303954
- PMCID
- PMC10829017
- ISSN
- 2041-6520
- eISSN
- 2041-6539
- Number of pages
- 10
- Grant note
- OAC-1626516 / U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry Program; United States Department of Energy (DOE) DE-SC0023022 / Basic Energy Sciences; United States Department of Energy (DOE) Royal Society for a University Research Fellowship; Royal Society URF\R1\211271 / NSF; National Science Foundation (NSF)
- Language
- English
- Date published
- 01/31/2024
- Academic Unit
- Chemistry
- Record Identifier
- 9984618636002771
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