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Rare earth benzene tetraanion-bridged amidinate complexes.
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 PDFLinear, Electron-Rich Erbium Single-Molecule Magnet with Dibenzocyclooctatetraene Ligands.
Inorg Chem
May 2024
Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States.
Judicious design of ligand scaffolds to highly anisotropic lanthanide ions led to substantial advances in molecular spintronics and single-molecule magnetism. Erbium-based single-molecule magnets (SMMs) are rare, which is attributed to the prolate-shaped Er ion requiring an equatorial ligand field for enhancing its single-ion magnetic anisotropy. Here, we present an electron-rich mononuclear Er SMM, [K(crypt-222)][Er(dbCOT)], (where dbCOT = dibenzocyclooctatetraene), that was obtained from a salt metathesis reaction of ErCl and KdbCOT.
View Article and Find Full Text PDFGold carbonyl cations and beyond: homoleptic gold(I) complexes with P and PS and the half-sandwich cation [Au(CH)(CO)].
Chem Commun (Camb)
May 2024
Albert-Ludwigs University Freiburg, Albertstr. 21, Freiburg 79104, Germany.
Oxidation of Au with the synergistic Ag/0.5 I system in the commercial organic solvent 1,2,3,4-tetrafluorobenzene led to the perfluoroalkoxyaluminate salt of the [Au(CO)] cation known from superacid chemistry. This [Au(CO)] salt proved to be an excellent 'naked' Au-synthon yielding complex salts with [Au(η-P)], [Au(η-PS)] and half-sandwich [Au(η-CH)(CO)] cation.
View Article and Find Full Text PDFOn-Surface Synthesis of Organolanthanide Sandwich Complexes.
Adv Sci (Weinh)
June 2024
Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanoscience), Madrid, 28049, Spain.
The synthesis of lanthanide-based organometallic sandwich compounds is very appealing regarding their potential for single-molecule magnetism. Here, it is exploited by on-surface synthesis to design unprecedented lanthanide-directed organometallic sandwich complexes on Au(111). The reported compounds consist of Dy or Er atoms sandwiched between partially deprotonated hexahydroxybenzene molecules, thus introducing a distinct family of homoleptic organometallic sandwiches based on six-membered ring ligands.
View Article and Find Full Text PDFTriple Inverse Sandwich versus End-On Diazenido: Bonding Motifs across a Series of Rhenium-Lanthanide and -Actinide Complexes.
Inorg Chem
April 2024
Department of Chemistry, University of California, Berkeley, California 94720, United States.
While synthesizing a series of rhenium-lanthanide triple inverse sandwich complexes, we unexpectedly uncovered evidence for rare examples of end-on lanthanide dinitrogen coordination for certain heavy lanthanide elements as well as for uranium. We begin our report with the synthesis and characterization of a series of trirhenium triple inverse sandwich complexes with the early lanthanides, Ln[(μ-η:η-Cp)Re(BDI)](THF) (, Ln = La, Ce, Pr, Nd, Sm; Cp = cyclopentadienide, BDI = ,'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate). However, as we moved across the lanthanide series, we ran into an unexpected result for gadolinium in which we structurally characterized two products for gadolinium, namely, (analogous to ) and a diazenido dirhenium double inverse sandwich complex Gd[(μ-η:η-N)Re(η-Cp)(BDI)][(μ-η:η-Cp)Re(BDI)](THF) ().
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