Divalent metallocenes of the lanthanides – a guideline to properties and reactivity

Abstract

A comprehensive overview of the syntheses, properties and reactivities of divalent metallocenes of the lanthanides is presented.

Get under the Umbrella: A Comprehensive Gateway for Researchers on Lanthanide‐Based Single‐Molecule Magnets

“…It can be complemented by the recent review of R. Layfield et al in 2022 [217] covering the last decade of organometallic 4 f-SMMs. Last, in 2023 [218] P. W. Roesky reviewed the properties and reactivity of divalent metallocenes for which little is known from the magnetic point of view.…”

Phenylsilyl-Substituted Tetramethylcyclopentadienide Uranium Chemistry: Magnesocenes vs Grignard Reagents

“…Solvent was removed under reduced pressure from the combined supernatant and washes to give HC 5 Me 4 (SiMe 2 Ph) as an orange oil (6.95 g, 87%). 1 3 mmol) was suspended in toluene (100 mL) to produce a white suspension. Ph 2 MeSiCl (6.73 g, 28.9 mmol) was added slowly via syringe to the KC 5 Me 4 H suspension at room temperature, and the resulting mixture was allowed to stir at room temperature for 2 days, turning from light brown to yellow.…”

“…Trituration of the residue with diethyl ether followed by drying under reduced pressure yielded [C 5 Me 4 (SiMe 2 Ph)MgCl(Et 2 O)] 2 , 4, as a white powder (0.55 g, 36%). X-ray quality crystals of 4 can be grown from slow diffusion of hexane into a toluene solution at −35 °C 1. H NMR (C 6 D 6 , 500 MHz): δ 7.60−7.59 (m, 4H, SiMe 2 Ph), 7.21−7.16 (m, 6H, SiMe 2 Ph), 3.42−3.38 (q, 8H, 3 J HH = 3.4 Hz, CH 3 CH 2 OCH 2 CH 3 ), 2.19 [s, 12H, C 5 Me 4 (SiMe 2 Ph)], 2.11 [s, 12H, C 5 Me 4 (SiMe 2 Ph)], 0.91−0.88 (t, 12H, 3 J HH = 0.9 Hz, CH 3 CH 2 OCH 2 CH 3 ), 0.75 (s, 12H, SiMe 2 Ph) ppm.…”

Tripodal tris(siloxide) ligand supported trivalent rare-earth metal complexes and redox reactivity

“…The chemistry of rare-earth metal complexes has witnessed impressive progress in the past two decades, not only in the discovery of new structural and bonding motifs, [1][2][3] but also in numerous aspects in catalysis. 4,5 Perhaps one of the most fascinating areas is the investigation of molecular rare-earth metal compounds with non-classical oxidation states, which would serve as the foundation for the development of new reactivities and applications of rare-earth metal compounds based on their electronic structures.…”