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. 2025 Feb 17;64(6):2795-2808.
doi: 10.1021/acs.inorgchem.4c04785. Epub 2025 Jan 31.

Multimetallic Half-Sandwich Complexes of the Rare-Earth Metals

Dennis A Buschmann  1 , H Martin Dietrich  1 , James Durrant  2 , Cäcilia Maichle-Mössmer  1 , Jinkui Tang  3 , Richard A Layfield  2 , Reiner Anwander  1
Affiliations

Multimetallic Half-Sandwich Complexes of the Rare-Earth Metals

Dennis A Buschmann et al. Inorg Chem. .

Abstract

Multimetallic half-sandwich complexes of the paramagnetic lanthanides gadolinium, terbium, dysprosium, holmium, and erbium as well as of diamagnetic yttrium are readily accessible via AlMe4/halogenido exchange reactions of Cp*Ln(AlMe4)2 with the mild halogenido transfer reagents Me3SiI and Me3GeX (Cp* = C5Me5; X = Br, Cl). Depending on the rare-earth-metal center and halogenido ion size, complexes with distinct structural motifs and nuclearities are obtained, including dimeric compounds [Cp*Ln(AlMe4)(μ2-Cl)]2 for the smaller metal centers Ln = Ho, Er, iodido-bridged tetranuclear rings [Cp*Ln(μ2-I)2]4 (Ln = Y, Tb, Dy, Ho, Er), and a heterobimetallic tetramethylaluminato-bridged gadolinium cluster [Cp*4Gd4I7(AlMe4)]2. The tetranuclear dysprosium complex [Cp*Dy(μ2-I)2]4 shows single-molecule magnet (SMM) behavior in zero applied field with an effective energy barrier of 164(10) cm-1.

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