Journal article
Investigations of the Electronic Structure of Arene-Bridged Diuranium Complexes
Organometallics, Vol.32(5), pp.1341-1352
03/11/2013
DOI: 10.1021/om3010367
Abstract
The electronic structure of the arene-bridged complex (mu-toluene)U-2(N[Bu-t]Ar)(4) (1a(2)-mu-toluene, Ar = 3,5-C6H3Me2) has been studied in relation to a variety of mononuclear uranium amide complexes, and their properties have been discussed comparatively. The syntheses, molecular structures (X-ray crystal structures and solution behavior based on variable-temperature NMR spectroscopic data), and corresponding spectroscopic (X-ray absorption near-edge structure and UV-vis-near-IR absorption) and magnetic properties are presented and interpreted with reference to results of density functional theory (DFT) and complete active space self-consistent field with corrections from second-order perturbation theory (CASSCF/CASPT2) calculations performed on model compounds. While the mononuclear compounds display expected electronic and magnetic properties for uranium complexes, 1a(2)-mu-toluene shows complicated properties in contrast. XANES spectroscopy, X-ray crystallography, and both density functional and CASSCF/CASPT2 results are consistent with the following electronic structure interpretation: f orbitals host the unpaired electrons, followed energetically by two delta bonds formed by filled uranium f orbitals and LUMOs of toluene.
Details
- Title: Subtitle
- Investigations of the Electronic Structure of Arene-Bridged Diuranium Complexes
- Creators
- Bess Vlaisavljevich - University of MinnesotaPaula L. Diaconescu - University of California, Los AngelesWayne L. Lukens - Lawrence Berkeley National LaboratoryLaura Gagliardi - University of MinnesotaChristopher C. Cummins - Massachusetts Institute of Technology
- Resource Type
- Journal article
- Publication Details
- Organometallics, Vol.32(5), pp.1341-1352
- Publisher
- Amer Chemical Soc
- DOI
- 10.1021/om3010367
- ISSN
- 0276-7333
- eISSN
- 1520-6041
- Number of pages
- 12
- Grant note
- CHE-9988806 / National Science Foundation; National Science Foundation (NSF) Packard Foundation; The David & Lucile Packard Foundation National Science Board; National Science Foundation (NSF) DE-SC002183 / DOE; United States Department of Energy (DOE) DE-AC02-05CH11231 / U.S. Department of Energy, Basic Energy Sciences, Chemical Sciences, Biosciences, and Geosciences Division; United States Department of Energy (DOE)
- Language
- English
- Date published
- 03/11/2013
- Academic Unit
- Chemistry
- Record Identifier
- 9984618644602771
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