Neutral inverse-sandwich rare-earth metal complexes of the benzene tetraanion

Wang, Yi; Zhang, Yurou; Liang, Jiefeng; Tan, Bowen; Deng, Chong; Huang, Wenliang

doi:10.1039/d4sc02491e

Chem. Sci.

2024

DOI: 10.1039/d4sc02491e

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Neutral inverse-sandwich rare-earth metal complexes of the benzene tetraanion

Yi Wang,

Yurou Zhang,

Jiefeng Liang

et al.

Abstract: Rare-earth metal complexes of the parent benzene tetraanion and neutral inverse-sandwich rare-earth metal arene complexes have remained elusive. Here, we report the first neutral inverse-sandwich rare-earth metal complexes of the...

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Cited by 6 publications

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Stabilization of the Compressed Planar Benzene Dianion in Inverse‐Sandwich Rare Earth Metal Complexes

Delano,

Demir

2024

Angewandte Chemie

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For the first time, the capture of a planar antiaromatic benzene dianion in between two trivalent rare earth (RE) metal cations, each stabilized by two guanidinate ligands, is reported. The synthesized inverse‐sandwich complexes [{(Me3Si)2NC(NiPr)2}2RE]2(µ–ƞ6:ƞ6–C6H6), (RE = Y (1), Dy (2), and Er (3)) feature a remarkably planar 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. In the 1H NMR spectrum of the diamagnetic Y complex 1, the equivalent proton resonance of the bridging benzene dianion ligand is drastically shifted to higher field in comparison to free benzene. This and the calculated highly positive Nucleus‐Independent Chemical Shift (NICS) values are attributed to the antiaromatic character of the benzene dianion ligand. The crucial role of the ancillary guanidinate ligand scaffold in stabilizing the planar benzene dianion conformation was also elucidated by DFT calculations. Remarkably, the planarity of the benzene dianion originates from the stabilization of the π‐type orbitals of the d‐manifold and compression through its strong electrostatic interaction with the two REIII sites.

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Stabilization of the Compressed Planar Benzene Dianion in Inverse‐Sandwich Rare Earth Metal Complexes

Delano,

Demir

2024

Angewandte Chemie

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Stabilization of the Compressed Planar Benzene Dianion in Inverse‐Sandwich Rare Earth Metal Complexes

Delano,

Demir

2024

Angew Chem Int Ed

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Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Ditert-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties

Klementyeva,

Gamer,

Schulze

et al. 2024

Inorg. Chem.

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The dinuclear β-diketiminato complex [L 1 ClDy(μ-Cl) 3 DyL 1 (THF)] (1) (L 1 = {2,6-i Pr 2 C 6 H 3 −NC(Me)CHC(Me)-N-2,6-i Pr 2 C 6 H 3 } − ) was obtained by reaction of DyCl 3 with KL 1 in a molar ratio of 1:1 and used for the preparation of the mixedligand complex [L 1 Dy(μ-3,5-Cat)] 2 (2) by salt metathesis reaction with 3,5-CatK 2 (3,5-Cat −3,5-di-tert-butyl-catecholate). Reactions of 3,5-CatNa 2 with [L 2 LnCl 2 (THF) 2 ] (Ln 3+ = Dy, Y) ligated with the less bulky ligand L 2 = {2,4,6-Me 3 C 6 H 2 − NC(Me)CHC(Me)N-2,4,6-Me 3 C 6 H 2 } − afforded the mixed-ligand THF-containing complexes [L 2 Ln(μ-3,5-Cat)(THF)] 2 (Ln 3+ = Dy (3a), Y ( 3b)). All new complexes were fully characterized, and the solid-state structures were determined by single-crystal X-ray diffraction. Magnetic measurements revealed single-molecule magnet behavior for the dysprosium complexes. Sub-Kelvin μSQUID studies confirm the SMM character of the systems, while CASSCF calculation along with simulation of the experimental data yields an antiferromagnetic interaction operating between the Dy 3+ ions.

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Neutral inverse-sandwich rare-earth metal complexes of the benzene tetraanion

Abstract: Rare-earth metal complexes of the parent benzene tetraanion and neutral inverse-sandwich rare-earth metal arene complexes have remained elusive. Here, we report the first neutral inverse-sandwich rare-earth metal complexes of the...

Cited by 6 publications

References 82 publications

Stabilization of the Compressed Planar Benzene Dianion in Inverse‐Sandwich Rare Earth Metal Complexes

Stabilization of the Compressed Planar Benzene Dianion in Inverse‐Sandwich Rare Earth Metal Complexes

Stabilization of the Compressed Planar Benzene Dianion in Inverse‐Sandwich Rare Earth Metal Complexes

Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Ditert-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties

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