New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]–. Issue 17 (9th September 2019)

• Record Type: Journal Article
• Authors: Harmgarth, Nicole; Liebing, Phil; Hilfert, Liane; Lorenz, Volker; Engelhardt, Felix; Busse, Sabine; Edelmann, Frank T.
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 645:Issue 17(2019)
• Page Start: 1101
• Page End: 1109
• Publication Date: 2019-09-09
• Subjects: Amidinate -- Lanthanides -- Cerium -- Structure elucidation; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201900141
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract : New homoleptic complexes of selected rare‐earth elements containing the unsymmetrically substituted amidinate ligand [MeC(NEt)(N t Bu)] – [= (L) – ] were synthesized and fully characterized. Treatment of in situ‐prepared Li(L) (1 ) with anhydrous lanthanide(III) chlorides, Ln Cl3 ( Ln = Sc, La, Ce, Ho), afforded three different types of amidinate complexes depending on the ionic radius of the central metal atom. The large La 3+ formed the octa‐coordinate DME solvate La(L)3 (DME) (2 ). Using Ce 3+, 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 Sc 3+ and Ho 3+ 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. Abstract :