854938-74-2

Upstream product

• 405885-00-9 N,N-2,6-diisopropylphenyl-2,4-pentanediimine ytterbium dichloride bis(tetrahydrofuran) 
• 1070-89-9 sodium hexamethyldisilazane 
• 108-88-3 toluene 

Downstream Products

• 854938-75-3 ClYb(CH(C(CH₃)NC₆H₃(CH(CH₃)2)2)2)OAl(CH₃)(CH(C(CH₃)NC₆H₃(CH(CH₃)2)2)2) 
• 1359735-43-5 [((2,6-iPr₂C₆H₃)NC(CH₃)CHCCH₂N(2,6-iPr₂C₆H₃))Yb(N(SiMe₃)2)(THF)]*toluene 

Relevant academic research and scientific papers

Synthesis of dianionic β-diketiminate lanthanide amides L′LnN(SiMe3)2THF by deprotonation of the β-diketiminate ligand L (L = {[(2,6- i Pr2C6H 3)NC(CH3)]2CH}-) and the transformation with [HNEt3][BPh4] to the cationic samarium amide [LSmN(SiMe3)2][BPh4]

Reaction of β-diketiminate lanthanide dichlorides LLnCl 2(THF)2 (L = {[(2,6-iPr2C6H 3)NC(CH3)]2CH}-) with 2 equiv of NaN(SiMe3)2 in toluene afforded lanthanide amide complexes supported by a dianionic β-diketiminate ligand L′, L′LnN(SiMe3)2(THF) (L′ ={(2,6-iPr 2C6H3)NC(CH2)CHC(CH 3)N(2,6-iPr2C6H3)}2-, Ln = Yb (1), Y (2), Gd (3), Sm (4)), in moderate yields via deprotonation of L. Addition of a small amount of THF led to an increase of the yields of 1-4. Lanthanide metals have a great influence on the deprotonation of L. The same reaction with LNdCl2(THF)2 did not afford the analogous complex L′NdN(SiMe3)2(THF), but the normal diamide complex LNd[N(SiMe3)2]2 (5) was isolated instead. The metathesis reaction of the triply bridged dichlorides of Sm, LSmCl(μ-Cl)3SmL(THF), with 2 equiv of NaN(SiMe3) 2 yielded the diamide complexes LSm[N(SiMe3) 2]2 in toluene, while complex 4 was formed instead in a mixture of toluene and THF. In contrast, the same reactions with LYbCl(μ-Cl)3YbL(THF) either in toluene or in a mixture of toluene and THF both afforded 1. Treatment of 4 with [HNEt3][BPh4] in THF at room temperature gave the novel cationic Sm β-diketiminate amide complex [LSmN(SiMe3)2(THF)2][BPh4] (7) in good yield. Complexes 1-5 and 7 have been confirmed by single-crystal X-ray structural analyses. The mechanism of deprotonation of L was discussed.

Synthesis of a new class of compounds containing a Ln-O-Al arrangement and their reactions and catalytic properties

Synthesis of a new class of compounds containing a Ln-O-Al moiety has been accomplished by the reaction of LAIOH(Me) (L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3) with a series of Cp3Ln compounds. The terminal AI-OH group shows selective reactivity, and the complexes Cp2Ln(THF)-O-AIL(Me) (Ln = Yb, 1; Er, 2; Dy, 3), Cp 2Yb-O-AIL(Me) (4), and Cp3Ln(μ-OH)AIL(Me) (Ln = Er, 5; Dy, 6; Sm, 7) were obtained. This allows further insight into the proton exchange process, and two different mechanisms, intermolecular and intramolecular elimination of CpH, are proposed under different conditions. Complexes 1-4, 6, and 7 have been characterized by X-ray structural analyses which reveals a Ln-O-Al or Ln(μ-OH)Al core in these complexes. The obtuse Ln-O-Al angles fall in the range 151.9-169.8°. The reaction of 1 or 4 with Me3SnF in toluene under refluxing conditions unexpectedly yielded the compounds [Cp2Yb-(μ-OSnMe3)]2 (8) and LAI(Me)F (9). Reactions of LAIOH(Me) with the mono- and dicyclopentadienyl complexes LYbCp(Cl) (10) and LYbCp2 (11) supported by the bulky β-diketiminate ligand were unsuccessful. However, the reaction of LAI(OH)Me with LYbN(SiMe3)2Cl (12) containing a labile Yb-N bond leads to the formation of LYbCl-O-AIL(Me) (13) under elimination of HN(SiMe 3)2. Furthermore, complexes 1, 3, 4, and 6 exhibit good catalytic activity for the polymerization of ε-caprolactone.