Abstract
Heterobimetallic µ2-imide complexes [Ho(µ2-Nmes*){Al(CH3)4}]2 (1, supermesityl = mes* = C6H2tBu3-2,4,6) and [Ho(µ2-Nmes*){Ga(CH3)4}]2 (2) have been synthesized from homoleptic complexes Ho[M(CH3)4]3 (M = Al, Ga) via deprotonation of H2Nmes* or with K[NH(mes*)] according to a salt metathesis-protonolysis tandem reaction. Single-crystal X-ray diffraction of isostructural complexes [Ho(µ2-Nmes*){M(CH3)4}]2 (M = Al, Ga) revealed asymmetric Ho2N2 metallacycles with very short Ho–N bond lengths and secondary Ho arene interactions.
Highlights
The emerging field of rare-earth metal imide chemistry has revealed interesting structural motifs [1,2], but studies regarding their fundamental properties and reactivity are lagging behind
While a series of dimeric Lewis acid (LA)-stabilized rare-earth metal imides has been reported previously [7], we report on additional aniline-derived rare-earth metal imide complexes employing methylaluminate and methylgallate complexes
Like the homoleptic tetramethylaluminate Ho[Al(CH3)4]3, the respective gallate complex can be converted into imido-bridged complexes [Ho{M(CH3)4}(μ2-Nmes*)]2 (M = Al (1), Ga (2))
Summary
The emerging field of rare-earth metal imide chemistry has revealed interesting structural motifs [1,2], but studies regarding their fundamental properties and reactivity are lagging behind. Bochkarev and Schumann were the first to report on a tetranuclear ytterbium(III) phenylimide complex obtainable via reduction of azobenzene by ytterbium naphthalenide [3]. Another synthesis strategy was developed by Evans et al, adventitiously identifying [Nd(NPh)(AlMe2)(AlMe4)2]2 (Figure 1, I) via attempted. We and others succeeded in the isolation of a series of rare-earth metal complexes (Figure 1, II–III, secondary interactions are not shown), by adopting the strategy of organoaluminum-assisted imide formation [5,6,7,8,9,10].
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