1435945-62-2Relevant academic research and scientific papers
Unprecedented reaction of bridged bis(guanidinate) lanthanide complexes: Sterically induced deprotonation
Wang, Chuanyong,Zhang, Xingmin,Xue, Mingqiang,Zhang, Yong,Shen, Qi
, p. 7009 - 7018 (2013)
Reaction of LnCl3 with a lithium salt of bridged bis(guanidinate) bearing a rigid naphthalene linker [Li2{LH 2}2Li2] (LH2 = 1,8-C 10H6{NC(NiPr)(NHiPr)}2) (1), which was synthesized by the reaction of 1,8-diaminonaphthalene with 2 equiv. of nBuLi, followed by treatment with 2 equiv. of N,N′-diisopropylcarbodiimide, yielded the chlorides [LnCl{LH2}] (Ln = Yb (2), Y (3)) in good yields. Metathesis reaction of 2 and 3 with NaN(SiMe3)2 did not afford the corresponding amide complexes, but the deprotonation products of [Ln{LH}]2 (LH = 1,8-C10H6{NC(NiPr)(NHiPr)}{NC(N iPr)2}; Ln = Yb (4), Y (5)) were isolated instead. The LH in 4 and 5 both act as a bridging ligand binding to two metals in a μ-η1:η2:η2 fashion, and the re-arrangement of LH occurred during the reaction. The size of the amido group was found to have a great influence on the outcome of the metathesis reaction. Reaction of 2 with bulky NaNH(C6H3iPr 2-2,6) afforded 4 as the only product, whereas the same reaction with less bulky LiNH(C6H4Cl-4) and LiNH(C6H 4CH3-4) led to the corresponding amides, [Yb{LH 2}(NHC6H4Cl-4)]2 (6) and [Yb{LH 2}(NHC6H4CH3-4)]2 (7), respectively. The re-arrangement of ligands was also observed in both cases. A possible pathway for the deprotonation of LH2 was discussed. Molecular structures of 1-7 were determined by X-ray single crystal analysis. The Royal Society of Chemistry 2013.
