Masked Divalent Reactivity of Heterobimetallic Lanthanide Isocarbonyl Complexes

A new rare‐earth reduction system is described in which trivalent yttrium and dysprosium react as though present in their unstable divalent oxidation state. This masked divalent reactivity is achieved using the isocarbonyl‐bridged dimers [( Cp2ttt ${{{\rm { Cp}}}_{{\rm { 2}}}^{{\rm { ttt}}}$ M)(μ‐Fp...

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Bibliographic Details
Published in:Angewandte Chemie International Edition Vol. 64; no. 7; pp. e202420207 - n/a
Main Authors: Mondal, Arpan, Tang, Jinkui, Layfield, Richard A.
Format: Journal Article
Language:English
Published: Germany Wiley Subscription Services, Inc 10.02.2025
Edition:International ed. in English
Subjects:
Dysprosium
Dysprosium compounds
Ligands
Magnetic properties
Oxidation
radical ligands
rare earth elements
Reactivity
single-molecule magnets
Valence
Yttrium
dysprosium
radical ligands
yttrium
single-molecule magnets
rare earth elements
ISSN:1433-7851, 1521-3773, 1521-3773
Online Access:Get full text
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Summary:A new rare‐earth reduction system is described in which trivalent yttrium and dysprosium react as though present in their unstable divalent oxidation state. This masked divalent reactivity is achieved using the isocarbonyl‐bridged dimers [( Cp2ttt ${{{\rm { Cp}}}_{{\rm { 2}}}^{{\rm { ttt}}}$ M)(μ‐Fp)]2 (M=Y, 1Y; M=Dy, 1Dy; Cpttt=1,2,4‐C5tBu3H2; Fp=CpFe(CO)2), where the reducing electrons originate from the bridging [Fp]− ligands. The reactivity of 1Y and 1Dy is showcased by reducing the N‐heterocycles 2,2′‐bipyridyl (bipy), phenazine (phnz) and hexaazatrinaphthylene (HAN) to give corresponding mono‐, di‐ and tri‐metallic rare‐earth complexes, respectively, with the heterocyclic ligands present in their singly, doubly and triply reduced forms, respectively. The dynamic magnetic properties of the dysprosium compounds are described. Compound 1Dy is a single‐molecule magnet (SMM) with an appreciable energy barrier of 449(17) cm−1, whereas [( Cp2ttt ${{{\rm { Cp}}}_{{\rm { 2}}}^{{\rm { ttt}}}$ Dy)2(μ‐phnz)] (3Dy) is not an SMM because of a strong, competing equatorial crystal field. Surprisingly, [( Cp2ttt ${{{\rm { Cp}}}_{{\rm { 2}}}^{{\rm { ttt}}}$ Dy)3(HAN)] (4Dy) is also not an SMM, the origins of which are traced to the impact of the tert‐butyl substituents on the dysprosium centre and its interaction with the radical [HAN]3− ligand. Using a mildly reducing organo‐iron ligand allows trivalent yttrium and dysprosium to react as though they were present in their less common divalent oxidation state. This masked divalent reactivity is used to reduce a series of N‐heterocycles, resulting in the formation of mono‐, di‐ or trimetallic lanthanide complexes of the reduced ligands.
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202420207