Journal article
An N-Tethered Uranium(III) Arene Complex and the Synthesis of an Unsupported U-Fe Bond
Organometallics, Vol.36(23), pp.4591-4599
12/11/2017
DOI: 10.1021/acs.organomet.7b00429
Abstract
Amination of 2,2 ''-dibromo-p-terphenyl with 2,6-diisopropylaniline, through Pd mediated cross coupling, yields the p-terphenyl bis(aniline) ligand H2LAr. Deprotonation of H2LAr with excess KH generates the dianion [K(DME)(2)](2)L-Ar as a dark red solid. Treatment of [K-(DME)(2)](2)L-Ar with UI3(dioxane)(1.5) produces the mononuclear U(III) complex (LU)-U-Ar(I)(DME) (1). Subsequent addition of the nucleophilic metal anion [CpFe(CO)(2)](-) (Fp(-)) gives the bimetallic U(III) compound (LU)-U-Ar(Fp) (2) in modest yield which features a rare instance of an unsupported U-M bond. Inspection of the metrical parameters of the solid-state structures of 1.DME and 2.0.5DME from X-ray crystallographic analyses show a seemingly eta(6)-interaction between the uranium and the terphenyl ligand (1: U1-C-centroid = 2.56 angstrom; 2: U1-C-centroid = 2.45 angstrom), spatially imposed as a consequence of the anilide N-donor atom coordination. Furthermore, the U-Fe bond length in 2 (U1-Fe1 = 2.9462(3) angstrom) is consistent with a metal-metal single bond. Notably, electronic structure analyses by CASPT2 calculations instead suggest that electrostatic, and not covalent, interactions dominate between the U-arene systems in 1 and 2 and between the U-Fe bond in the latter.
Details
- Title: Subtitle
- An N-Tethered Uranium(III) Arene Complex and the Synthesis of an Unsupported U-Fe Bond
- Creators
- Skye Fortier - Univ Texas El Paso, Dept Chem, El Paso, TX 79968 USAJ. Rolando Aguilar-Calderon - Univ Texas El Paso, Dept Chem, El Paso, TX 79968 USABess Vlaisavljevich - University of South DakotaAlejandro J. Metta-Magana - Univ Texas El Paso, Dept Chem, El Paso, TX 79968 USAAlan G. Goos - Univ Texas El Paso, Dept Phys, El Paso, TX 79968 USACristian E. Botez - Univ Texas El Paso, Dept Phys, El Paso, TX 79968 USA
- Resource Type
- Journal article
- Publication Details
- Organometallics, Vol.36(23), pp.4591-4599
- Publisher
- Amer Chemical Soc
- DOI
- 10.1021/acs.organomet.7b00429
- ISSN
- 0276-7333
- eISSN
- 1520-6041
- Number of pages
- 9
- Grant note
- 1205302 / Direct For Mathematical & Physical Scien; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) ACS-PRF 57132-DNI3 / ACS; American Cancer Society University of Texas at El Paso 64705CHREP; 67290CHREP / U.S. Department of Defense Army Research Office; United States Department of Defense AH-1922-20170325 / Welch Foundation; The Welch Foundation DMR-1205302 / NSF PREM; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS)
- Language
- English
- Date published
- 12/11/2017
- Academic Unit
- Chemistry
- Record Identifier
- 9984618507802771
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