Lanthanides and actinides : Annual survey of their organometallic chemistry covering the year 2000

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2016

The reactivities and chemoselectivities of sodium diisopropylamide (NaDA) in N,N-dimethylethylamine (DMEA) are compared with those of lithium diisopropylamide (LDA) in tetrahydrofuran (THF). Metalations of arenes, epoxides, ketones, hydrazones, dienes, and alkyl and vinyl halides are represented. The positive attributes of NaDA–DMEA include high solubility, stability, resistance to solvent decomposition, and ease of preparation. The high reactivities and chemoselectivities often complement those of LDA–THF.

/pdf/sodium-diisopropylamide-in-n-n-dimethylethylamine-reactivity-2mea722xif.pdf

Sodium Diisopropylamide in N,N-Dimethylethylamine: Reactivity, Selectivity, and Synthetic Utility

Alkali metal naphthalenide or anthracenide reacted with scandium(III) anilides [Sc(X){N(tBu)Xy}2 (thf)] (X=N(tBu)Xy (1); X=Cl (2); Xy=C6 H3 -3,5-Me2 ) to give scandium complexes [M(thf)n ][Sc{N(tBu)Xy}2 (RA)] (M=Li-K; n=1-6; RA=C10 H82- (3-Naph-K) and C14 H102- (3-Anth-M)) containing a reduced arene ligand. Single-crystal X-ray diffraction revealed the scandium(III) center bonded to the naphthalene dianion in a σ2 :π-coordination mode, whereas the anthracene dianion is symmetrically attached to the scandium(III) center in a σ2 -fashion. All compounds have been characterized by multinuclear, including 45 Sc NMR spectroscopy. Quantum chemical calculations of these intensely colored arene complexes confirm scandium to be in the oxidation state +3. The intense absorptions observed in the UV/Vis spectra are due to ligand-to-metal charge transfers. Whereas nitriles underwent C-C coupling reaction with the reduced arene ligand, the reaction with one equivalent of [NEt3 H][BPh4 ] led to the mono-protonation of the reduced arene ligand.

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.202000946

Reduced Arene Complexes of Scandium

In contrast to previously applied salt metathesis protocols the targeted rare-earth-metal compounds Ln[N(SiMe3)2]2(halogenido) were accessed by oxidation of Ln(II) silylamide precursors. Treatment of Sm[N(SiMe3)3]2(thf)2 with 0.5 equiv of C2Cl6 or 0.25 equiv of TeBr4 in thf and crystallization thereof gave [Sm{N(SiMe3)2}2(μ-X)(thf)]2 (X = Cl, Br). A similar reaction/crystallization procedure performed with 0.5 equiv of 1,2-diiodoethane gave monomeric Sm[N(SiMe3)2]2I(thf)2. Switching to Yb[N(SiMe3)2]2(thf)2, the aforementioned oxidants generated monomeric five-coordinate complexes Yb[N(SiMe3)2]2X(thf)2 (X = Cl, Br, I). The reaction of Eu[N(SiMe3)2]2(thf)2 with 0.5 equiv of C2Cl6 in thf yielded the separated ion pair [Eu{N(SiMe3)2}3Cl][(thf)5Eu(μ-Cl)2Eu(thf)5]. Performing the chlorination in n-hexane led to oxidation followed by rapid disproportionation into EuCl3(thf)x and Eu[N(SiMe3)2]3. The bromination reaction did not afford crystalline material, while the iodination gave crystals of divalent EuI2(thf)5...

Trivalent Rare-Earth-Metal Bis(trimethylsilyl)amide Halide Complexes by Targeted Oxidations.

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.

/pdf/synthesis-and-structural-diversity-of-trivalent-rare-earth-4epn0e3zlm.pdf

Synthesis and structural diversity of trivalent rare-earth metal diisopropylamide complexes

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Synthesis and structural diversity of trivalent rare-earth metal diisopropylamide complexes