Synthesis, Structural Characterization, and Reactivity of Lanthanide Complexes Containing a New Methylene-Bridged Indenyl-Pyrrolyl Dianionic Ligand
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- 作者：Chengfu Pi ; Zhengxing Zhang ; Ruiting Liu ; Linhong Weng ; Zhenxia Chen ; Xigeng Zhou
- 刊名：Organometallics
- 出版年：2006
- 出版时间：October 9, 2006
- 年：2006
- 卷：25
- 期：21
- 页码：5165 - 5172
- 全文大小：186K
- 年卷期：v.25,no.21(October 9, 2006)
- ISSN：1520-6041
文摘
A new methylene-bridged ligand incorporating both indenyl and pyrrolyl moieties, (C9H7)CH2(
-C4H3NH) (1), was prepared. Reaction of LnI2 with 1 equiv of [(C9H6)CH2(-C4H3N)]Li2(THF)x in THF,followed by recrystallization in DME, gave the organolanthanide(II) complexes {(
5-C9H6)CH2[
-1:5-(-C4H3N)]Ln(DME)}2 (Ln = Sm (2), Yb (3)) in mederate yields. Treatment of SmCl3 with 1 equivof [(C9H6)CH2(-C4H3N)]Li2(THF)x in THF gave the trivalent organosamarium chloride {(5-C9H6)CH2[-1:5-(-C4H3N)]Sm(-Cl)2Li(THF)2}2 (4) in 73% yield, while reaction of ErCl3 with [(C9H6)CH2(-C4H3N)]Li2(THF)x under the same conditions generated [(5-C9H6)CH2(-1:3-C4H3N)Er(3-Cl)(-Cl)Li(THF)2]2 (5). Reaction of 4 with 2 equiv of n-butyllithium (nBuLi) and subsequently with N,N'-dicyclohexylcarbodiimide (CyN=C=NCy) gave the carbodiimide insertion into the Sm-C bond product{(5-C9H6)CH2[-1:5-(-C4H3N)]Sm[CyNC(nBu)NCy]}2 (6), while treatment of 4 with 2 equiv of NaN(SiMe3)2 in THF followed by reacting with CyN=C=NCy gave the carbodiimide insertion into the Sm-Nbond product [(5-C9H7)CH2[-1:5-(-C4H3N)]Sm{CyNC[N(SiMe3)2]NCy}]2 (7). These complexes werecharacterized by IR and 1H NMR spectra and elemental analyses. Furthermore, the structures of all thesecompounds were also confirmed by X-ray diffraction analyses.
-C4H3NH) (1), was prepared. Reaction of LnI2 with 1 equiv of [(C9H6)CH2(-C4H3N)]Li2(THF)x in THF,followed by recrystallization in DME, gave the organolanthanide(II) complexes {(5-C9H6)CH2[-1:5-(-C4H3N)]Ln(DME)}2 (Ln = Sm (2), Yb (3)) in mederate yields. Treatment of SmCl3 with 1 equivof [(C9H6)CH2(-C4H3N)]Li2(THF)x in THF gave the trivalent organosamarium chloride {(5-C9H6)CH2[-1:5-(-C4H3N)]Sm(-Cl)2Li(THF)2}2 (4) in 73% yield, while reaction of ErCl3 with [(C9H6)CH2(-C4H3N)]Li2(THF)x under the same conditions generated [(5-C9H6)CH2(-1:3-C4H3N)Er(3-Cl)(-Cl)Li(THF)2]2 (5). Reaction of 4 with 2 equiv of n-butyllithium (nBuLi) and subsequently with N,N'-dicyclohexylcarbodiimide (CyN=C=NCy) gave the carbodiimide insertion into the Sm-C bond product{(5-C9H6)CH2[-1:5-(-C4H3N)]Sm[CyNC(nBu)NCy]}2 (6), while treatment of 4 with 2 equiv of NaN(SiMe3)2 in THF followed by reacting with CyN=C=NCy gave the carbodiimide insertion into the Sm-Nbond product [(5-C9H7)CH2[-1:5-(-C4H3N)]Sm{CyNC[N(SiMe3)2]NCy}]2 (7). These complexes werecharacterized by IR and 1H NMR spectra and elemental analyses. Furthermore, the structures of all thesecompounds were also confirmed by X-ray diffraction analyses.