| Abstract: | New homoleptic complexes of selected rare‐earth elements containing the unsymmetrically substituted amidinate ligand [MeC(NEt)(NtBu)]– [= (L)–] were synthesized and fully characterized. Treatment of in situ‐prepared Li(L) ( 1 ) with anhydrous lanthanide(III) chlorides, LnCl3 (Ln = Sc, La, Ce, Ho), afforded three different types of amidinate complexes depending on the ionic radius of the central metal atom. The large La3+ formed the octa‐coordinate DME solvate La(L)3(DME) ( 2 ). Using Ce3+, the octa‐coordinate “ate” complex Li(THF)[Ce(L)4] ( 3 ) was formed. Depending on the crystallization conditions, compound 3 could be crystallized in two modifications differing in the coordination environment around Li. In the case of the smaller Sc3+ and Ho3+ ions, six‐coordinate homoleptic Sc(L)3 ( 4 ) and Ho(L)3 ( 5 ) were isolated. The title compounds were fully characterized by spectroscopic and analytical methods as well as single‐crystal X‐ray diffraction. With Ln = La and Ce, several by‐products incorporating lithium, chlorine and/or oxygen were also isolated and structurally characterized. |
