Homoleptic cerium(IV) diisopropylamide was synthesized via oxidation of ate complex Ce(NiPr2)4Li(thf) with trityl chloride or hexachloroethane. Due to its ready accessibility, and high pKa value of the proligand HNiPr2, Ce(NiPr2)4 features a promising candidate for protonolysis reactions, as shown for the synthesis of dimeric cerium(IV) tetrakis(1,1,3,3-N,N,N',N'-tetramethylguanidinate).

A series of rare-earth metal diisopropylamide complexes has been obtained via salt metathesis employing LnCl3(THF)x and lithium (LDA) or sodium diisopropylamide (NDA) in n-hexane. Reactions with AM : Ln ratios ≥3 gave ate complexes (AM)Ln(NiPr2)4(THF)n (n = 1, 2; Ln = Sc, Y, La, Lu; AM = Li, Na) in good yields. For smaller rare-earth metal centres such as scandium and lutetium, a Li : Ln ratio = 2.5 accomplished ate-free tris(amido) complexes Ln(NiPr2)3(THF). The chloro-bridged dimeric derivatives [Ln(NiPr2)2(μ-Cl)(THF)]2 (Ln = Sc, Y, La, Lu) could be obtained in high yields for Li : Ln = 1.6-2. The product resulting from the Li : La = 1 : 1.6 reaction revealed a crystal structure containing two different molecules in the crystal lattice, [La(NiPr2)2(THF)(μ-Cl)]2·La(NiPr2)3(THF)2. Recrystallization of the chloro-bridged dimers led to the formation of the monomeric species Ln(NiPr2)2Cl(THF)2 (Ln = Sc, Lu) and La(NiPr2)3(THF)2. The reaction of YCl3 and LDA with Li : Y = 2 in the absence of THF gave a bimetallic ate complex LiY(NiPr2)4 with a chain-like structure. For scandium, the equimolar reactions with LDA or NDA yielded crystals of tetrametallic mono(amido) species, {[Sc(NiPr2)Cl2(THF)]2(LiCl)}2 and [Sc(NiPr2)Cl2(THF)]4, respectively. Depending on the Ln(iii) size, AM, and presence of a donor solvent, ate complexes (AM)Ln(NiPr2)4(THF)n show distinct dynamic behaviour as revealed by variable temperature NMR spectroscopy. The presence of weak LnCH(iPr) β-agostic interactions, as indicated by Ln-N-C angles <105°, is corroborated by DFT calculations and NBO analysis.

Rare-earth metal diisopropylamide complexes LiLn(NiPr)(THF) (Ln = Sc, Y, La), [LiY(NiPr)], NaLn(NiPr)(THF) (Ln = Sc, Y), Sc(NiPr)(THF) and Ce(NiPr) were screened as catalysts for the intramolecular hydroamination/cyclization (IHC) of 1-amino-2,2-dimethyl-4-pentene, 1-amino-2,2-diphenyl-4-pentene, and 1-amino-2,2-diphenyl-5-hexene at ambient and moderately increased temperature of 60 °C in CD. The lithium ate complexes displayed the most efficient precatalysts with high conversion rates at 60 °C for the phenyl-substituted substrates and Ln = Y and La, affording turnover frequencies N as high as 164 h. The catalytic activity could be increased by employing THF-free complex [LiY(NiPr)] (N = 45.8 h at 26 °C; 34.1 h for LiY(NiPr)(THF)). In situ generation of putative LiY(NiPr)(THF) from YCl(THF) and four equivalents of LiNiPr (LDA) in CD generated a catalyst revealing N comparable to pre-isolated crystallized LiY(NiPr)(THF) but yielding even higher substrate conversion. The IHC reactions were also examined for rare-earth metal bis(trimethylsilyl)amide catalysts Ln[N(SiMe)] (Ln = Sc, Y, La) as well as for LDA using the same reaction conditions, revealing overall superior activity of the silylamide derivatives but poor performance of LDA compared to the rare-earth metal diisopropylamide complexes LiLn(NiPr)(THF). Cyclization of 1-amino-2,2-diphenyl-5-hexene to the 6-membered heterocycle 2-methyl-4,4-diphenylpiperidine by lanthanum derivative LiLa(NiPr)(THF) was accompanied by a competitive isomerization reaction affording max. 20% of 1-amino-2,2-diphenyl-4-hexene after 2 h at 60 °C. Crystalline tetravalent Ce(NiPr) showed a better IHC performance than crystalline trivalent Sc(NiPr)(THF) as preliminary examined for 1-amino-2,2-diphenyl-4-pentene at 26 °C (N = 5.6 and 0.9 h, respectively), but cyclization came to a halt after 2 h, probably due to decomposition of the catalyst.