Using previously established salt‐metathesis procedures at low temperature, heterobimetallic ate complexes Li6EuII(n‐Bu)8(thf)6 and Li3YIII(i‐Bu)6(thf)4 could be synthesized and their solid‐state structures analyzed by X‐ray diffraction. Recently described complex Li3Y(n‐Bu)6(thf)4 was probed as a precursor in protonolyses with various amines, revealing distinct reaction pathways. Identified products comprise homoleptic amide Y[HNC6H3(mes)2‐2,6]3 (mes=C6H2Me3‐2,4,6), heteroleptic C−H‐bond activated Li3Y(n‐Bu)2[N(SiMe2CH2)(C6H3‐Me2‐3,5)]2(thf)5, and mixed amido/imido complex [LiY2(HNSiPh3)4(NSiPh3)2][Li(thf)2(OEt2)2].
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