([2,6-([2,6-(i-Pr)2C6H3]N-C=(CH2))2(C5H3N)]NdCl2(DME))(Li(DME)3] | 784143-29-9

• 英文名称: ([2,6-([2,6-(i-Pr)2C6H3]N-C=(CH2))2(C5H3N)]NdCl2(DME))(Li(DME)3]
• CAS: 784143-29-9
• 化学式: C₁₂H₃₀LiO₆*C₃₇H₅₁Cl₂N₃NdO₂
• 分子量: 1062.28
• InChiKey: UKWNRMXTYXRRQI-UHFFFAOYSA-L

反应信息

• 作为产物：
  描述：

  乙二醇二甲醚 、 ([2,6-([2,6-(i-Pr)2C6H3]N-C=(CH2))2(C5H3N)]Nd(THF))(μ-Cl)2[Li(THF)2]*0.5(hexane) 以 乙二醇二甲醚 为溶剂， 以76%的产率得到([2,6-([2,6-(i-Pr)2C6H3]N-C=(CH2))2(C5H3N)]NdCl2(DME))(Li(DME)3]
  参考文献：
  名称：

  Preparation of an Active Neodymium Catalyst for Regioselective Butadiene cis-Polymerization Supported by a Dianionic Modification of the 2,6-Diiminopyridine Ligand

  摘要：

  Treatment of the 2,6-diiminopyridine ligand 2,6-{[2,6-(i-Pr)(2)C6H3]N=C(CH3)}(2)(C5H3N) with 2 equiv of Me3SiCH2Li afforded the corresponding {[2,6-{[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)](2-) (1) dianion via deprotonation of the two methyl groups attached to the two imine functions. Reaction of 1 with NdCl3(THF)(3) yielded {[2,6-{[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd(THF)}(mu-Cl)(2)[Li(THF)(2)](.)0.5(hexane) (2a), whose recrystallization from DME gave the corresponding ionic {[2,6-{[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]NdCl2(DME)}{Li(DME)(3)] (2b). With the exception of the reaction with (allyl)MgBr, which proceeded readily with 2b to form the allyl derivative {[2,6-{[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd(eta(3)-C3H5)Br}{Li(DME)(3)} (3), compounds 2a,b are not suitable starting substrates for further alkylation reactions. A viable synthetic strategy for the preparation of alkyl derivatives of 2 consisted instead of the pretreatment of NdCl3(THF)(3) with RLi [R = Me3SiCH2, CH3] at low T followed by treatment with either the diimine ligand or 1. According to this procedure, the terminally bound alkyl derivative [2,6-{[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd[CH2Si(CH3)(3)](THF) (4) was prepared and subsequently crystallographically characterized. The same synthetic procedure with MeLi afforded {[2,6-{[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd}(mu-CH3)(2)[Li(THF)(2)] (5) and {[2,6-{[2,6-(i-Pr)(2)C6H3]N-C=(CH2)}(2)(C5H3N)]Nd}(mu-Cl)(mu-X)[Li(THF)(2)] (6) [X = Cl 53%, Me 47%] depending on the MeLi/Nd ratio. Both 5 and 6 as well as 2a are potent catalysts for the cis-polymerization of butadiene.

  DOI：

  10.1021/om0496434