Reduction of [U(Ts(Tol))(Cl)(μ-Cl)U(Ts(Tol))(THF)2] [2, Ts(Tol) = HC(SiMe2NAr')3; Ar' = 4-MeC6H4)] with KC8 in toluene afforded the new arene-bridged diuranium complex [{U(Ts(Tol))}2(μ-η(6):η(6)-C6H5Me)] (3); combined structural, spectroscopic, magnetic, and computational analyses unambiguously confirm that the uranium centres in 3 are in the +5 oxidation state and the toluene is a 10π-tetraanion.
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http://dx.doi.org/10.1039/c3dt50255d | DOI Listing |
Chem Sci
December 2024
Frontier Institute of Science and Technology, State Key Laboratory of Electrical Insulation and Power Equipment, MOE Key Laboratory for Nonequilibrium Synthesis of Condensed Matter, Xi'an Key Laboratory of Electronic Devices and Materials Chemistry and School of Chemistry, Xi'an Jiaotong University 99 Yanxiang Road Xi'an Shaanxi 710054 P. R. China
The benzene tetraanion-bridged rare earth inverse arene amidinate complexes [{Ln(κ:η-Piso)}(μ-η:η-CH)] (2-Ln, Ln = Gd, Tb, Dy, Y; Piso = {(NDipp)C Bu}, Dipp = CH Pr-2,6) were prepared by the reduction of parent Ln(iii) bis-amidinate halide precursors [Ln(Piso)X] (Ln = Tb, Dy; X = Cl, I) or [Ln(Piso)I] (Ln = Gd, Y) with 3 eq. KC in benzene, or by the reaction of the homoleptic Ln(ii) complexes [Ln(Piso)] (Ln = Tb, Dy) with 2 eq. KC in benzene.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
Aromatic organometallic complexes, such as ferrocene and the "inverse sandwich complex" [NaCp], are stabilized via charge-transfer (C-T) interactions and cation-π interactions (i.e., charge-induced dipole and charge-quadrupole interactions).
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
A series of dilanthanide benzene inverse sandwich complexes of the type (CpLn)(μ-η:η-CH) () (Ln = Y, Gd, Tb, Dy, Tm) are reported. These compounds are synthesized by reduction of the respective trivalent dimers CpLnI (Ln = Y, Gd, Tb, Dy, Tm) in diethyl ether with potassium graphite in the presence of benzene, and they feature an unusual linear coordination geometry with a highly planar benzene bridge as verified by single-crystal X-ray diffraction. The Ln-Bz distances of are the shortest distances observed to date, ranging from 1.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan, 48824, USA.
For the first time, the capture of the planar antiaromatic parent benzene dianion in between two trivalent rare earth (RE) metal cations (RE), each stabilized by two guanidinate ligands, is reported. The synthesized inverse-sandwich complexes [{(MeSi)NC(NPr)}RE](μ-η : η-CH), (RE=Y (1), Dy (2), and Er (3)) were crystallized from aprotic solvents and feature a remarkably planar parent benzene dianion, previously not encountered for any metal ion prone to low or absent covalency. The -2 charge localization at the benzene ligand was deduced from the results obtained by single-crystal X-ray diffraction analyses, spectroscopy, magnetometry, and Density Functional Theory (DFT) calculations.
View Article and Find Full Text PDFInorg Chem
September 2024
Aiiso Yufeng Li Family Department of Chemical and Nano Engineering, University of California, San Diego, La Jolla, California 92093, United States.
Traditional σ, π, and δ types of covalent chemical bonding have been extensively studied for nearly a century. In contrast, ϕ-type bonding involving f ( = 4, 5) orbitals has received less attention due to their high contraction and minimal orbital overlap. Herein, we theoretically predict a singly occupied ϕ···ϕ bonding between two 5f orbitals, facilitated by B group orbitals in the hexa-boron diuranium inverse sandwich structure of UB.
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