Synthese und Reaktivität von diskreten Calciumimiden

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Discrete organoimide complexes of the divalent rare-earth metals samarium, europium, and ytterbium are reported. Tandem salt metathesis-protonolysis reactions using Ln bis(tetramethylaluminate) precursors [Ln(AlMe ) ] and monopotassium salts of 2,6-diisopropylaniline (H NDipp) and triphenylsilylamine prove viable and efficient protocols. Depending on the ionic radius of the Ln metal centers and the steric demand of the imido carbon backbone, mono- and dilanthanide arrangements of general composition [(thf) Ln(NR)(AlMe )] (Ln=Sm, Eu, Yb; R=Dipp, SiPh ) are found in the solid state. Complex formation and stabilization is achieved by coordination of the Lewis acid AlMe , which also prevents formation of higher aggregated species. The feasibility of redox chemistry is shown with the plumbocene derivative Cp* Pb, providing access to the corresponding monomeric Ln half-sandwich complexes [Cp*Ln(NR)(AlMe )(thf) ] (Ln=Sm, Yb).

Lewis‐Acid Stabilized Organoimide Complexes of Divalent Samarium, Europium, and Ytterbium

Wolf

Stuhl

Maichle‐Mößmer

et al. 2018

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

Thim

Schädle

Maichle‐Mößmer

2018

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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.

Chasing Multiple Bonding Interactions between Alkaline‐Earth Metals and Main‐Group Fragments

Wolf

Anwander

2019

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Formally dianionic ligands such as alkylidenes or organoimidos play a major role in the organometallic chemistry of transition metals and are an emerging topical area of f‐element chemistry. The pursuit and development of main‐group‐metal congeners has been tackled sporadically but is clearly lacking behind. The pronounced ionic bonding in particular, prevailing in alkali and alkaline‐earth (Ae) metal derivatives, proved cumbersome. Recent substantial progress in the respective field of divalent Ae chemistry has been triggered by the implementation of new synthesis strategies involving new AeII precursors and tailor‐made ligands. The main emphasis of this Minireview will be on the synthesis and reactivity of well‐defined Group 2 alkylidenes, organoimides, silylenes, and phosphandiides.