Rare‐Earth Metal Diimide Complexes via Alkylaluminate Templating, Including a Ceric Derivative

Abstract

Protonolysis of lanthanide tris(tetramethylaluminate)s with two equivalents of 2,6-diisopropylaniline affords La III and Ce III diimide compounds Ln[(m-NC 6 H 3 iPr 2 -2,6) 2 AlMe 2 ](thf) 4 featuring ab identate AlMe 2 -linked diimido ligand. As revealed for the corresponding Ce(GaMe 4 ) 3reaction, formation of the diimidec omplexes proceedsv ia tetrametallic complexes of the type[ Ce{(m-NC 6 H 3 iPr 2 -2,6)(HNC 6 H 3 iPr 2 -2,6)(MMe 3 )}] 2 (Me = Al, Ga). Oxidation of the cerium(III) complexw ith hexachloroethanel eads to a neutralC e IV diimides pecies. Partialp rotonolysis with phenylacetylene andh ydrogenolysis via H 3 SiPh give conclusive insights into the reactive coordination sites of such diimidec omplexes.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

Triisobutylaluminium-promoted formation of lanthanide hydrides

“…28 Compared to our work, this may suggest that two aluminato units may be involved. Further, the comparison of interatomic distances clearly shows similarities of 1 Nd with the calculated parameters reported by Guo et al 26,28 They describe substitution of the Nd-O for Nd-C bonds, which are in the range of 2.57-2.58 Å. We observed strikingly similar Nd-C interatomic distances in the range of 2.542-2.763 Å for 1 Nd .…”

“…[1][2][3] For example, Cui et al )(m-H)AlMe 2 ](thf) 3 }] 2 features a La-H-Al linkage, but NMR spectroscopic data were not provided. 26 Variable temperature 1 H-NMR spectra performed on 1 La revealed highly fluxional isobutyl groups, i.e. the resonances of bridging and terminal isobutyl groups do not exhibit decoalescence even at 193 K (cf.…”

Lanthanoid Biphenolates as a Rich Source of Lanthanoid‐Main Group Heterobimetallic Complexes

“…Again, the Ln−O bond lengths of the bridging oxygens are significantly longer than their non‐bridging counterparts. Analogous rare earth‐aluminium biphenolate bimetallics with the general form [AlMe 2 Ln(mbmp) 2 (thf) 2 ] (Ln=Y, [14] and Sm [16] ) have been reported, the former from reaction of an isolated [Y(mbmp)(mbmpH)(thf) 3 ] complex and there are analogous lanthanum‐ and cerium‐aluminium based anilido complexes [19] …”

“…Analogous rare earth-aluminium biphenolate bimetallics with the general form [AlMe 2 Ln(mbmp) 2 (thf) 2 ] (Ln = Y, [14] and Sm [16] ) have been reported, the former from reaction of an isolated [Y(mbmp)(mbmpH)(thf) 3 ] complex and there are analogous lanthanum-and cerium-aluminium based anilido complexes. [19] Complex 18 is an ionic compound, comprised of a sevencoordinate, distorted pentagonal bipyramidal lanthanum cation and a four-coordinate, distorted tetrahedral aluminium anion (Figure 9). The lanthanum atom is ligated by one mbmp 2À ligand, one oxygen in an axial, and the other in an equatorial position (O(1)-La(1)-O(2) = 92.93(7)°) and five thf molecules, one in an axial, and four in equatorial positions.…”

“…On the other hand, the second methylene CÀ H and the closest H of the Scheme 4. Reaction of a partially protonated, mononuclear Gd complex with potassium bis(trimethylsilyl)amide to yield a GdÀ K bimetallic complex (19). tBu group are too distant to be considered an interaction.…”