Reduction of Hexaazatrinaphthylenes by Masked Divalent Lanthanide Dinitrogen Reagents

Mondal, A, Price, CGT, Steiner, A ORCID: 0000-0002-4315-6123, Tang, J ORCID: 0000-0002-8600-7718 and Layfield, RA ORCID: 0000-0002-6020-0309 (2025) Reduction of Hexaazatrinaphthylenes by Masked Divalent Lanthanide Dinitrogen Reagents Inorganic Chemistry, 64 (26). pp. 13309-13317. ISSN 0020-1669, 1520-510X

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Abstract

The oxidation state +2 is of interest in rare-earth chemistry since it allows these conventionally redox-inactive metals to be used as reducing agents. However, the divalent oxidation state is difficult to form for most rare-earth elements, and the ensuing compounds are often unstable. Here, we describe an approach to rare-earth reduction chemistry that circumvents the divalent oxidation state by using compounds of trivalent rare earths that store reducing electrons on the dinitrogen ligand [N<inf>2</inf>]^2-, akin to “masked” divalent reactivity. Thus, the dinitrogen complexes (Formula presented) (1<inf>M</inf>, M = Y, Gd, Tb, Dy, Cp^ttt = 1,2,4-C<inf>5</inf>^tBu<inf>3</inf>H<inf>2</inf>) reduce hexaazatrinaphthylene and its hexamethyl derivative to give trimetallic (Formula presented), where the [R<inf>6</inf>HAN]^3- ligands (R = H, 2<inf>M</inf>; R = Me, 3<inf>M</inf>) form with S = 1/2, and with elimination of N<inf>2</inf>. The structures of 2<inf>M</inf> and 3<inf>M</inf> reveal that the tert-butyl substituents strongly influence the core geometry of these trimetallic complexes. Analysis of the magnetism and electronic structure of 2<inf>Gd</inf> and 3<inf>Gd</inf> identifies ferromagnetic metal-radical exchange, with coupling constants of J = +2.87 cm^-1 and +3.07 cm^-1, respectively (−2J formalism). The unusual ferromagnetic exchange is a consequence of charge transfer to the gadolinium 5d, 6s, and 6p orbitals from the radical ligands.

Item Type:	Article
Uncontrolled Keywords:	3402 Inorganic Chemistry, 34 Chemical Sciences
Divisions:	Faculty of Science & Engineering Faculty of Science & Engineering > School of Physical Sciences Faculty of Science & Engineering > School of Physical Sciences > Chemistry
Depositing User:	Symplectic Admin
Date Deposited:	20 Feb 2026 08:08
Last Modified:	28 Feb 2026 16:45
DOI:	10.1021/acs.inorgchem.5c01681
Open Access URL:	https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c0...
Related Websites:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3197129
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